Facile Construction of Mechanically Robust CO ₂ -Based Degradable Polymers with Self-Healing and Shape Memory via Thioctic Acid Inverse Vulcanization

Transforming carbon dioxide (CO2) into value-added polymeric materials represents a promising strategy for achieving carbon neutrality and sustainable advanced materials. However, the structural diversity and functionality of existing CO2-based polymers remain limited, particularly for multifunctional material systems. Herein, we report a facile and sustainable strategy to construct a CO2-derived covalent adaptable network (CAN) by incorporating dynamic disulfide bonds via inverse vulcanization with the biobased small molecule thioctic acid (TA). A degradable allyl-functionalized polycarbonate precursor was first synthesized through terpolymerization of CO2, propylene oxide, and allyl glycidyl ether, followed by direct cross-linking with TA to form dynamically disulfide-linked networks without the need for elaborately designed cross-linkers. The resulting materials exhibit pronounced self-strengthening during healing, yielding self-healable polymers that combine robustness, large elongation, and a healing efficiency ∼110% when 10 wt % TA is incorporated, superior to most previously reported biobased and degradable self-healing polymers. Moreover, the polymers display thermal reprocessability and body-temperature-triggered reconfigurable shape memory behavior. This work provides a synthetically simple and multifunctional CAN platform, expanding the design gallery and application potential of the CO2-based polymers.