Coagulative Nucleation in the Copolymerization of Methyl Methacrylate–Butyl Acrylate under Monomer-Starved Conditions

Coagulative nucleation in the copolymerization of methyl methacrylate–butyl acrylate (MMA-BA) via semicontinuous emulsion heterophase polymerization (SEHP) under monomer-starved conditions in latexes with high solid content (50.0 wt %) and low concentrations of surfactant is reported. The SEHP technique allows the obtention of latex with high colloidal stability and has potential industrial application in polymer synthesis. High instantaneous conversions (>90%) and a high-ratio polymerization rate/addition rate (Rp/Ra) ≥ 0.9 were obtained at low times until the final copolymerization, which confirmed the starved conditions in the systems at the highest surfactant concentrations. The particle size exhibited a linear size increment at conversions between 0 and 40% induced by homogeneous nucleation, a transition region between 40 and 50%, and non-linear behavior at higher conversions by coagulative nucleation. These three behaviors were also observed in the particle surfactant coverage area (Sc), Z-potential, particle coagulation rate (dNp/dt) by the Smoluchowski model, final particle size (Dpz), and number particle (Np) through the reaction. By means of transmission electron microscopy (TEM) images, the onset of coagulation was observed from 50% of conversion until the end of the reaction. In addition, in both processes of copolymerization, tacticity was displayed (mainly syndiotacticity).