New shape memory polymers with self‐healing behavior are obtained by thermoreversible Diels–Alder (DA) cross‐linking of a furfuryl group‐containing star‐block copolymer with 1,1′‐(methylenedi‐4,1‐phenylene)bismaleimide. The star‐block copolymer consisting of a 3‐arm polycaprolactone (PCL) core and a polyfurfuryl methacrylate shell is synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. For this, a 3‐arm macro‐RAFT agent based on PCL is converted with an appropriate amount of furfuryl methacrylate in the presence of a radical initiator. Films of the DA network are partly insoluble at ambient temperatures. After annealing at 120 °C the films become completely soluble because of the progressing retro‐DA reaction. Evaporation of the solvent and subsequent annealing at 60 °C restores the original insoluble state of the material. By means of a scratch test and tensile tests on cut and subsequently mended samples it is shown that the retro‐DA reaction facilitates self‐healing. Additionally, the films show pronounced shape memory effects with reasonable shape recovery and fixity ratios, which are attributed to the melting and crystallization of the PCL phase.

中文翻译：

---

基于动态共价化学的具有自愈和形状记忆双重特性的量身定制的功能性聚甲基丙烯酸甲酯

通过含糠基的星形嵌段共聚物与1,1'-（亚甲基二-4,1-亚苯基）双马来酰亚胺的热可逆Diels-Alder（DA）交联，可获得具有自愈性能的新型形状记忆聚合物。通过可逆加成-断裂链转移（RAFT）聚合合成由3-臂聚己内酯（PCL）核和聚甲基丙烯酸糠基酯壳组成的星形嵌段共聚物。为此，在自由基引发剂存在下，将基于PCL的3臂Macro-RAFT剂与适量的甲基丙烯酸糠酯转化。DA网络的薄膜在环境温度下部分不溶。在120°C退火后，由于逆向DA反应的进行，薄膜变得完全可溶。蒸发溶剂并随后在60°C下退火，可恢复材料的原始不溶状态。通过对切割后的样品进行划痕测试和拉伸测试，可以证明RetroDA反应有助于自我修复。此外，薄膜还具有明显的形状记忆效果，并具有合理的形状恢复率和固定率，这归因于PCL相的熔融和结晶。