Green Stereoregular Polymerization of Poly(methyl methacrylate)s through Vesicular Catalysis

Abstract

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.