To bridge the gap between thermoplastics and thermosets, covalent adaptive networks (CANs) utilize reversible bimolecular small molecule chemistry to adapt to different stimuli though dynamic bond exchanges. We propose that by changing this bimolecular process into intramolecular rearrangement in network polymers could lead to a new type of material with enhance mechanical properties. Bullvalene became the ideal molecular Rubik’s cube in this application for it goes through constant low-barrier Cope Rearrangements making its substituents “fluctuates” between multiple isomers of bullvalene. In this work, we demonstrated the compatibility of bullvalene and radical initiated polymerization conditions and study the effect of bullvalene as a side chain in the thermal properties of polyacrylates. We reported the first bullvalene containing fluxional crosslinked material and studied the effect of Cope rearrangements in polymer networks. Through thermal and mechanical testings, we garnered the initial results for such novel fluxional crosslinked materials potential as a new type of impact resistance, shape memory materials.

Using fluxional small molecule to access the next generation covalent adaptive materials

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ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.