Stereoselective polymerization can yield polymers with specific tacticity and properties, and it is an essential topic throughout polymer synthesis history. Herein, we report for the first time on a vesicular catalysis method to realize the green stereoregular polymerization of isotactic-rich poly(methyl methacrylate) (PMMA) in water and at ambient temperature and pressure, namely by conducting the polymerization of MMA monomers in the confined 5-10 nm thick hydrophobic layers of hyperbranched polymer vesicles. The isotactic degree of the as-prepared PMMAs increases from 12% to 40% with the decrease of vesicle size from 840 to 85 nm in hydrodynamic diameter (Dh) due to the conformation confinement effect of MMA monomers inside the thin vesicle membranes through a curvature-dependent way. The present work has extended the scope of green chemistry, and it also represents a new application of polymer vesicles in stereoregular polymerization. © 2022 CCS Chemistry. All rights reserved.
