Side Chain Dispersity Matters: Topologically Precise and Discrete Bottlebrush Polymers

The synthesis of bottlebrush polymers with topologically precise and fully discrete structures is reported. Key features of the synthesis include the combination of scalable synthesis and separation strategies to access discrete macromonomer libraries, followed by their polymerization and further separation into topologically uniform and discrete bottlebrushes. Discrete macromonomers prove crucial for regulating the structural heterogeneity of bottlebrushes and their macroscopic properties. When assembled as a monolayer at the air-water interface, bottlebrushes with discrete side chains display high packing density and distinct three-phase Langmuir-Blodgett isotherms. The impact of precisely regulating side chain dispersity and sequence on polymer properties was further demonstrated through tailoring the interbrush interactions and thermomechanical properties of well-defined block bottlebrushes.