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• W2008032148 abstract "Abstract Thiol‐isocyanate‐acrylate ternary networks were formed by the combination of thiol‐isocyanate coupling, thiol‐acrylate Michael addition, and acrylate homopolymerization. This hybrid polymerization reaction sequence was preferentially controlled by using phosphine catalyst systems in combination with photolysis. The reaction kinetics of the phosphine/acrylate thiol‐isocyanate coupling reactions were systematically investigated by evaluating model, small molecule reactions. The thiol‐isocyanate reaction was completed within 1 min while the thiol‐acrylate Michael addition reaction required ∼10 min. Both thiol‐isocyanate coupling and thiol‐acrylate Michael addition reactions involving two‐step anionic processes were found to be both quantitative and efficient. However, the thiol‐isocyanate coupling reaction was much more rapid than the thiol‐acrylate Michael addition, promoting initial selectivity of the thiol‐isocyanate reaction in a medium containing thiol, isocyanate, and acrylate functional groups. Films were prepared from thiol‐isocyanate‐acrylate ternary mixtures using 2‐acryloyloxyethylisocyanate and di‐, tri‐, and tetra‐functional thiols. The sequential thiol‐isocyanate, thiol‐acrylate, and acrylate homopolymerization reactions were monitored by infrared spectroscopy during film formation, whereas thermal and mechanical properties of the films were evaluated as a function of the chemical composition following polymerization. The results indicate that the network structures and material properties are tunable over a wide range of properties ( T g ∼ 14–100 °C, FWHM ∼ 8–46 °C), while maintaining nearly quantitative reactions, simply by controlling the component compositions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3255–3264, 2010" @default.
• W2008032148 created "2016-06-24" @default.
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• W2008032148 date "2010-06-25" @default.
• W2008032148 modified "2023-10-18" @default.
• W2008032148 title "Thiol-isocyanate-acrylate ternary networks by selective thiol-click chemistry" @default.
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• W2008032148 doi "https://doi.org/10.1002/pola.24102" @default.
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