Effects of glutaric anhydride functionalization on filler-free benzoxazine/epoxy copolymers with shape memory and self-healing properties under near-infrared light actuation

Abstract

We have developed new types of thermosets from bio-based benzoxazine/epoxy copolymers with shape memory and self-healing properties that could be triggered by using near-infrared (NIR) light, without using any filler. The copolymers were prepared from bio-based raw materials, including vanillin, furfurylamine, and epoxidized castor oil, along with functionalized with glutaric anhydride (GA), due to which self-healing properties of the copolymers were enabled through dynamic covalent bonds. Effects of GA content (0.00, 0.02, 0.04, 0.06, 0.08, and 0.10 mol) on molecular structure, mechanical properties, dynamic mechanical properties, and thermal stability of the copolymers were investigated. The results from infrared spectroscopy showed the formation of ester linkages and free carboxylic acids upon functionalization of copolymers with GA. The increased crosslinking density by GA was observed from increased tensile strength (from 11 to 16 MPa), glass transition temperature (72–150 °C), and degradation temperature at 5% weight loss (382–405 °C) of the copolymers. However, excess contents (0.08 and 0.10 mol) of GA might result in the existence of free components, hindering the formation of the copolymer network and diminishing the mechanical properties of the copolymers. Shape memory properties of GA-functionalized V-fa/ECO copolymers were investigated under NIR actuation; the results showed a 100% of shape recovery ratio within 20 s of actuation. Self-healing properties of GA-functionalized V-fa/ECO copolymers were investigated under NIR actuation; the results showed 94% of restored storage modulus after 20 min of actuation. Lastly, the self-healing mechanism under NIR actuation was proposed that NIR photothermal effects of the copolymers induced the crack closing due to their shape memory effects. Consequently, the copolymer chains could diffuse across the crack interface along with transesterification through GA functionalities, leading to crack healing. The findings of this study suggested a new way to produce NIR light-responsive self-healing polymer without using NIR photothermal filler. • Filler-free benzoxazine/epoxy copolymers with shape memory and self-healing effects triggered by NIR light were developed. • Copolymers were synthesized from bio-based raw materials and functionalized with glutaric anhydride (GA). • Copolymers showed 100% shape recovery within 20 s and 94% restored storage modulus after 20 min of NIR light actuation. • Self-healing mechanism involved shape memory effects and transesterification induced by NIR photothermal effects.