Solvent-free preparation of carbon fiber reinforced dynamically cross-linked vanillin-based polyurethane composites with excellent self-healing and closed-loop recycling performance

Disposing of the wastes generated from the carbon fiber reinforced polymer (CFRP) composite materials after service failure has attracted great attention in recent years. CFRP composites prepared with dynamically covalent cross-linking polymers as matrix resins possess excellent self-healing and recyclability performance, providing an efficient solution to overcome this challenge. However, most of the dynamic cross-linking resins are typically made by high-cost petroleum-derived compounds with extensive use of organic solvents and environmentally unfriendly catalysts. Herein, catalyst-free self-healing and recyclable vanillin-based polyurethanes (V-PUs) via dynamic phenol-carbamate bonds were synthesized by a one-step solvent-free method with a biodegradable PCL as soft segment and biobased vanillin derivative as the chain extender. The optimized V-PUs exhibit Young's modulus of 1.92 GPa, stress at break of 64.98 MPa, glass transition temperature of 95 °C, and over 90 % self-healing and reprocessing efficiency. This excellent self-healing and reprocessing performance can be successfully transferred to the CFRP composite materials fabricated with the V-PUs as matrix resins by hand paste-vacuum bag pressing method. The interlayer shear strength (ILSS) of the composite material is 41 MPa, and the healing efficiency determined by ILSS reaches 85.34 %. Closed-loop recovery of the carbon fiber and matrix resin from the CFRP composite is realized through the solvent dissolution approach due to the dynamic character of the phenol-carbamate bonds, which is of great significance for the development of green economy and sustainable society.