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Thiol–Ene Linear Step-Growth Photopolymerization in Miniemulsion: Fast Rates, Redox-Responsive Particles, and Semicrystalline Films

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journal contribution
posted on 02.02.2016, 00:00 by Florent Jasinski, Agnès Rannée, Julie Schweitzer, Diane Fischer, Emeline Lobry, Céline Croutxé-Barghorn, Marc Schmutz, Didier Le Nouen, Adrien Criqui, Abraham Chemtob
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.