Abstract: To alleviate the pressure on the petrochemical industry and address environmental concerns, the utilization of polyurethane (PU) derived from castor oil (CO) (as an ester polyol replacement of petrochemical-based materials) has garnered significant attention in recent decades. Extending the service life of materials requires imparting self-healing properties to vegetable oil-based polymers, an aspect that has received limited attention in current studies. However, low self-healing efficiency still poses a significant challenge, and non-conductivity also remains an obstacle in current research, crucial for their application in electronic devices. In this work, we present the first series of electrically self-healing biopolymer composites constructed by incorporating carbon nanotube (CNT) networks into crosslinked castor oil-based polyurethane (BPU) through a simple curing process. These materials address the challenges mentioned above and exhibit improved mechanical, electrical, and self-healing capabilities compared to other bio-based self-healing materials. The resulting BPU/CNT composite demonstrated exceptional repeated self-healing capacity, restoring both mechanical properties and electrical performance even after experiencing severe mechanical damage. Notably, this composite served as a conductive substrate in flexible solid-state supercapacitor (FSSC) devices. Consequently, the FSSC derived from the composite conductive substrate achieved an impressive 92.4 % self-healing efficiency even after undergoing 7 cutting/healing cycles. The device remained virtually unchanged even after being bent at a 180° angle with a bending radius of 1.6 mm, indicating excellent repeatability and durability. The exceptional self-healing ability, with ∼98 % electrical recovery at 100 °C for 70 s and 93 % at 80 °C after 6 min, of these composites was attributed to the synergistic interactions of the dynamic exchange reactions of disulfide bonds and dense hydrogen bonds within the BPU matrix, which provide a reversible dynamic polymer network. The healing efficiency of these dynamic bonds was evaluated by adjusting the composition ratio of the long linear chain of pTHF in hybrid polyols of the crosslinked polymer network. Overall, this work highlights a series of green, simple, and highly efficient self-healing polymer composites derived from renewable castor oil, and it establishes an essential framework for future sustainable polymer composite design.

Key words: Natural oils, Castor oil-based polyurethane, Self-healing, Conductivity, Flexible supercapacitor