Abstract
Radical polymerization of N-isopropylacrylamide (NIPAAm) in toluene was investigated in the presence of bidentate Lewis base such as diphosphonates. Isotacticity of the obtained poly(NIPAAm)s slightly increased at −80 °C, whereas syndiotactic-rich poly(NIPAAm)s were obtained at −40–0 °C. This result corresponded to the results observed in the presence of primary alkyl phosphates. NMR analysis revealed that NIPAAm monomer and tetraisopropyl methylenebisphosphonate formed mono-binding hydrogen-bond-assisted complex at 0 °C, but a chelate complex at −80 °C. Thus, it was concluded that the stereospecificity in NIPAAm polymerization strongly depended on the complexation mode of the added bidentate Lewis base.
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