Biobased photothermal responsive shape memory polythioether/MXene nanocomposites with self-extinguishing performance

Thermosetting shape memory polymers (TS-SMPs) have a higher shape fixity ratio ( R f ) and shape recovery ( R r ) due to their structure integrity and thermal stability, and the glass transition temperature ( T g ) usually influences the transition temperature ( T trans ) of TS-SMPs. Therefore, it is significant to tailor the T g range and mechanical properties for TS-SMPs. In this work, the inherently flame-retarding bio-based MXene-reinforced polythioether nanocomposites with excellent shape memory performance, driven by photothermal response, were designed. Firstly, a photopolymerizable MXene nanomonomer (MPS-MXene) was obtained by introducing 3-(methacryloxy) propyltrimethoxysilane onto the surface of the MXene monolayer. Then, the bis(4-allyl-2-methoxyphenyl) phenyl phosphonate (BEP) was synthesized by eugenol (a lignin derivative) with phenyl phosphonic dichloride. The polythioether/MXene composites (BEP-T- x M) were synthesized through in-situ thiol-ene photopolymerization of MPS-MXene, BEP, and tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate. Surprisingly, compared with neat polythioether, the T g of BEP-T-0.2 M composite increased from 19.6 to 34.6 °C, when only 0.2 wt% MPS-MXene was added. The photothermal conversion efficiency ( η  = 73.8 %) and shape memory performance with R r (>98 %) were greatly improved. Consequently, the interesting phenomena such as “sunflowers growing towards the sunlight” and “thermal shrinkage” can be observed. Meanwhile, the tensile strength and Young’s modulus increased significantly by 141 % and 91 %, respectively, due to the good dispersion of rigid MPS-MXene nanosheets. Furthermore, all the polythioether/MXene composites showed self-extinguishing performance. This study will provide a novel strategy for designing biobased photothermal-responsive TS-SMPs.