Radical step-growth photopolymerization of dithiol–diene monomer miniemulsion is shown to be a highly efficient, robust, and versatile route to generate film-forming linear poly(thioether) latexes. At extremely fast rates, the process results in high-molecular-weight polysulfide products, exhibiting both semicrystalline and oxidation-responsive properties. Four key issues are addressed as regards the practical implementation of this novel UV-driven waterborne technology: the preparation of a photolatent and colloidally stable thiol–ene monomer miniemulsion, the identification of key experimental parameters controlling reaction kinetics and polymer microstructure, the characterization of film semicrystallinity, and the application of poly(thioether ester) latexes as dual-stimuli-responsive nanocarriers sensitive to both oxidation and hydrolysis.

An efficient continuous synthesis of nanolatex was achieved in water using a single-lane photochemical microreactor combined with an energy-saving and safe UV fluorescent lamp. Acrylate and thiol-ene miniemulsions were polymerized in high yields at low irradiance (3 mW cm⁻²) upon controlling droplet size, temperature and residence time.