A General Synthesis of Cyclic Bottlebrush Polymers With Enhanced Mechanical Properties via Graft-Through Ring Expansion Metathesis Polymerization

Bottlebrush polymers represent an important class of macromolecular architectures, with applications ranging from drug delivery to organic electronics. While there is an abundance of literature describing the synthesis, structure, and applications of linear bottlebrush polymers using ring-opening metathesis polymerization (ROMP), there are comparatively less reports on their cyclic counterparts. This lack of research is primarily due to the difficulty in synthesizing cyclic bottlebrush polymers, as extensions of typical routes towards linear bottlebrush polymers (i.e., “grafting-through” polymerizations of macromonomers with ROMP) produce only ultrahigh molar mass cyclic bottlebrush polymers with poor molar mass control. Herein, we report a ring-expansion metathesis polymerization (REMP) approach to cyclic bottlebrush polymers via a “grafting-through” approach utilizing the active pyr-CB6 initiator developed in our lab. The resulting polymers, characterized via GPC-MALS-IV, are shown to have superior molar mass control across a range of target backbone lengths. The cyclic materials are also found to have superior mechanical properties when compared to their linear counterparts, as assessed by ball-mill grinding and compression testing experiments.