Direct synthesis of syndiotactic-rich poly(N-isopropylacrylamide) via radical polymerization of hydrogen-bond-complexed monomer |
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Authors: | Tomohiro Hirano Hitomi Miki Makiko Seno Tsuneyuki Sato |
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Affiliation: | Department of Chemical Science and Technology, Faculty of Engineering, Tokushima University, Minamijosanjima 2-1, Tokushima 770-8506, Japan |
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Abstract: | Radical polymerization of N-isopropylacrylamide (NIPAAm) in toluene was investigated in the presence of hexamethylphosphoramide (HMPA). We succeeded in directly preparing syndiotactic-rich poly(NIPAAm), the syndiotacticity of which (r=70%) is the highest among those of radically-prepared poly(NIPAAm)s so far reported, by lowering polymerization temperature to −60 °C in the presence of a two-fold amount of HMPA. The NMR analysis revealed that the induced syndiotactic-specificity was ascribed to 1:1 complex formation between NIPAAm and HMPA. Furthermore, thermodynamic analysis described that the induced syndiotactic-specificity was enthalpically achieved. |
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Keywords: | N-Isopropylacrylamide Hydrogen bond Stereospecific radical polymerization |
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