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

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 ( = 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.