INS14-0940
Electronic Control of C–C Bond Cleavability in Depolymerizable Polymer Backbones
Topic
S14. The 2nd PSK / CCS-PD Joint Symposium on Frontiers in Polymer Science and Engineering
When and Where
Oct 1, 2026
12:00 - 12:25
Room 203
Session Chairs
Hui Joon PARK
Presenter(s)
Bumjoon Seo (Seoul National University of Science and Technology)
Co-Author(s)
Abstract
The problem of recycling commodity polymers is being actively addressed through physical, chemical, and biological approaches, as well as their combinations. In parallel, constructing a circular economy for commercial polymers requires molecular-level design principles that can be considered at the polymer design stage, so that efficient depolymerization is built into the backbone structure from the outset. Most successful examples of chemical recycling to monomer have relied on heteroatom-containing linkages or strained cyclic structures, where depolymerization is promoted by relatively weak bonds or favorable ring-opening/ring-closing equilibria. In this work, we instead examine how local electronic effects can be used to control the cleavability of formally strong C–C bonds in polymer backbones. Density functional theory calculations are used to evaluate how β-unsaturation, lone-pair donation, hyperconjugation, and carbonyl-adjacent substitution modify radical stability and bond dissociation energies. Butadiene-derived repeat units serve as the primary model system for identifying selective intermonomer C–C bond weakening, while acetyl-substituted structures are included as representative motifs for extending the same design logic beyond simple polybutadiene analogs. Several of the proposed structures have been synthesized and polymerized, providing experimental support for the computationally derived trends.
