Time-Resolved Small-Angle X-ray Scattering Studies during the Aqueous Emulsion Polymerization of Methyl Methacrylate

Recently, we reported time-resolved synchrotron small-angle X-ray scattering (TR-SAXS) studies during aqueous emulsion polymerization using a bespoke stirrable reaction cell (J. Am. Chem. Soc. 2021, 143, 1474-1484). This proof-of-concept study utilized a semifluorinated specialty monomer (2,2,2-trifluoroethyl methacrylate) to ensure high X-ray contrast relative to water. Herein, we extend this approach to emulsion polymerization of methyl methacrylate (MMA) in the presence or absence of sodium dodecyl sulfate (SDS) at 70 °C. Solution conductivity measurements for this anionic surfactant indicated a critical micelle concentration (CMC) of 10.9 mM at this temperature. Thus, SDS was employed at either 1.0 or 20.0 mM, which corresponds to well below or well above its CMC. Postmortem analysis by ¹H NMR spectroscopy indicated MMA conversions of 93-95% for these three formulations. We demonstrate that the X-ray contrast between water and PMMA is sufficiently large to produce high-quality scattering patterns during TR-SAXS experiments. Such patterns were fitted using a hard-sphere scattering model to monitor the evolution in particle diameter. This enabled (i) determination of the time point for the onset of nucleation and (ii) the evolution in particle size to be monitored during the MMA polymerization. The final particle diameters obtained from such TR-SAXS studies were consistent with postmortem DLS analyses, while TEM studies confirmed that near-monodisperse latex particles were formed. Micellar nucleation occurs within just 2 min when the SDS concentration is well above its CMC, resulting in a high particle number concentration and relatively small latex particles. In contrast, when SDS is either absent or present below its CMC, particle nuclei are formed by homogeneous nucleation over significantly longer time scales (14-15 min). In the latter case, adsorption of SDS onto nascent particles reduces their coagulation, giving rise to a larger number of smaller particles compared to the surfactant-free polymerization. However, the characteristic time required for the onset of nucleation is barely affected because this is mainly controlled by the kinetics of homogeneous polymerization of the relatively water-soluble MMA monomer within the aqueous phase. These results suggest that the aqueous emulsion polymerization of several other (meth)acrylic monomers, and perhaps also vinyl acetate, may be amenable to TR-SAXS studies.