As the complexity of polymer structure grows, so do the challenges for developing an accurate understanding of their structure–property relationships. Here, the synthesis of bottlebrush polymers with topologically precise and fully discrete structures is reported. A key feature of the strategy is the synthesis of discrete macromonomer libraries for their polymerization into topologically precise bottlebrushes that can be separated into discrete bottlebrushes ( Đ = 1.0). As the system becomes more discrete, packing efficiency increases, distinct three-phase Langmuir−Blodgett isotherms are observed, and its glass transition temperature becomes responsive to side-chain sequence. Overall, this work presents a versatile strategy to access a range of precision bottlebrush polymers and unravels the impact of side-chain topology on their macroscopic properties. Precise control over side chains opens a pathway for tailoring polymer properties without changing their chemical makeup.

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.