Topologically Precise and Discrete Bottlebrush Polymers: Synthesis, Characterization, and Structure–Property Relationships

[Image: see text] 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.