Molecular-scale observation of formation of nuclei in soap-free polymerization of styrene

To clarify the mechanism of the nucleation process in the soap-free polymerization of styrene in water, the polymerization process of styrene mainly at a temperature 46 degrees C was investigated on a molecular scale using an atomic force microscope (AFM) as well as a scanning electron microscope (SEM) and a dynamic light scattering apparatus (DLS). A cationic initiator was employed to make polymerized styrene adsorb electrostatically on the negatively charged mica plate with molecular-scale smoothness, and the mechanism was estimated from their AFM measurements in situ in water. The following was found. There exist two streams to produce PSL particles in the polymerization: one is the polymerization in monomer droplets fragmented by mixing from the main monomer reservoir floating above the solution, and the other is the polymerization of monomers dissolved in the solution by initiators. The former is normally neglected or not recognized because of the small contribution. The latter is the main production process of PSL particle, which is investigated in detail on a molecular scale, and a possible mechanism was proposed.