Development of NIR light-responsive shape memory composites based on bio-benzoxazine/bio-urethane copolymers reinforced with graphene

Abstract

In this work, shape memory polymers (SMPs) were developed from a combination of a bio-based benzoxazine (BZ) monomer and polyurethane prepolymer (PU-prepolymer), both derived from bio-based raw materials. The bio-based BZ monomer (V-fa monomer) was synthesized through a Mannich condensation reaction using vanillin, paraformaldehyde, and furfurylamine. The bio-based PU-prepolymer was obtained by reacting palm oil polyol (MW = 1400 Da) and toluene diisocyanate (TDI). To investigate the curing behavior of poly(V-fa/urethane), with a mass ratio of 50/50, differential scanning calorimetry was employed. The structure of the resulting poly(V-fa/urethane) was confirmed using Fourier transform infrared spectroscopy. Furthermore, the synthesized V-fa/urethane copolymers with weight ratios of 70/30, 60/40, 50/50 and 40/60 were observed to exhibit shape memory behaviors induced by near-infrared irradiation (808 nm). Poly(V-fa/urethane), specifically with a mass ratio of 50/50, demonstrated superior shape memory performance. It exhibited a remarkable capacity to retain the temporary shape up to 90%, achieve 99% shape recovery, and exhibit a recovery time of 25 s. The shape memory properties were further improved with the addition of 3 wt% graphene nanoplatelets (GNPs), exhibiting an improvement in the shape fixity value to 94%, and shape recovery time value to 16 s. Moreover, our findings suggest that 60/40 poly(V-fa/urethane) reinforced with 3 wt% GNPs possesses favorable characteristics for applications as multiple SMPs, with shape fixity values of 97% and 94%, and shape recovery values of 96% and 89% for the first and second shapes, respectively.