Polymerization of Styrene in Cyclodextrin Channels: Can Confined Free‐Radical Polymerization Yield Stereoregular Polystyrene?

Summary: Modeling of polystyrenes (PS) with various stereosequences in the narrow cylindrical channels corresponding to those found in γ‐cyclodextrin inclusion compounds (CD ICs) has been conducted. Based on the conformational modeling of stereoisomeric polystyrenes (PSs) in narrow channels, it was suggested that polystyrene with unusual microstructures might be produced by the constrained polymerization of styrene monomer in its γ‐CD‐IC crystals. The in‐situ polymerization of styrene inside the narrow channels of its γ‐CD‐IC crystals was performed in both organic and aqueous media. The 13C NMR spectrum of PS synthesized inside the γ‐CD channels in an aqueous medium shows some differences when compared to the 13C NMR spectrum of PS synthesized in toluene. These are presumably because of differences in their stereosequences. Here, we report our preliminary findings. Schematic of cyclodextrin inclusion compound (CD‐IC) channels with included polymer guests. magnified image Schematic of cyclodextrin inclusion compound (CD‐IC) channels with included polymer guests.