ORGS3-0021
Cooperative reactivity in polymer mechanochemistry
Topic
GS3. Graduate Student Oral Session III: Polymer Synthesis, Structure, Properties, and Processing
When and Where
Sep 28, 2026
16:36 - 16:48
Room 103
Session Chairs
Jiwon KIM
Junmin LEE
Youngwoon KO
Presenter(s)
Vittal Bhat (Stanford University)
Co-Author(s)
Abstract
Polymer mechanochemistry typically concerns the transformation of isolated mechanophores upon application of force. Our group recently reported a poly(benzobarrelane) ROMP polymer in which electronic coupling between repeat units allows continuous segments of mechanophores to undergo cascade reactivity and transform the polymer backbone, while isolating repeat units from each other shuts down the mechanochemical reactivity. This design conceptually distinguishes poly(benzobarrelane) from previous mechanophore-containing polymers. Here we show that this type of reactivity can be generalized to a class of common ROMP polymers, poly(endo-tricyclodecadiene)s. Subjecting these polymers to mechanical force induces radical cascade reactivity along the backbone, leading to unzipping of the repeat units to transform the backbone structure. Furthermore, chemically generating radicals on the mechanochemically transformed polymer backbone in the absence of force enables reversion to the original poly(endo-tricyclodecadiene) structure, as a consequence of the principle of microscopic reversibility. This work demonstrates a new design paradigm for reversible covalent polymer backbone transformation under orthogonal conditions or stimuli.
