Precise Synthesis of Poly(methyl methacrylate) Brush with Well-Controlled Stereoregularity Using a Surface-Initiated Living Anionic Polymerization Method

Densely grafted polymer brushes, which consist of end-tethered chains that are predominantly oriented perpendicular to the substrate, show a number of unique functional properties due to their highly organized structure. Controlling the stereoregularity of the main chain while maintaining a high grafting density offers further opportunities to increase the density of functional sites through the formation of cavities within the brush structure. Concentrated poly(methyl methacrylate) (PMMA) brushes with well-controlled stereoregularity and polydispersity index (PDI) were prepared on flat and spherical substrates using a surface-initiated living anionic polymerization method in the presence of triethylaluminum (AlEt₃). The syndiotactic PMMA brush forms with helical chains and is able to encapsulate C₆₀ molecules within the formed cavities.