Dynamic Imine Bond-Based Shape Memory Polymers with Permanent Shape Reconfigurability for 4D Printing

• Published in: ACS applied materials & interfaces Vol. 11; no. 43; pp. 40642 - 40651
• Main Authors: Miao, Jia-Tao, Ge, Meiying, Peng, Shuqiang, Zhong, Jie, Li, Yuewei, Weng, Zixiang, Wu, Lixin, Zheng, Longhui
• Format: Journal Article
• Language: English
• Published: American Chemical Society 30.10.2019
• Subjects: dynamic covalent bond; 4D printing; reconfiguration; shape memory; (meth)acrylate
• ISSN: 1944-8244; 1944-8252
• DOI: 10.1021/acsami.9b14145

Shape memory polymer (SMP)-based 4D printing combines the advantages of SMP and 3D printing to form active materials with delicate structure. Nowadays, studies of SMP-based 4D printing materials mainly focus on cross-linked (meth)­acrylate of which the permanent shape cannot be changed for their covalent linkage, limiting the usage of 4D printing materials. In this paper, a novel (meth)­acrylate monomer with an aldehyde group (2-(methacryloyloxy)­ethyl 4-formylbenzoate, MEFB) and hyperbranched cross-linker (HPASi) are synthesized to build (meth)­acrylate systems (IEMSis) with dynamic imine bonds for 4D printing. The flexible chain structure of HPASi significantly enhances the toughness of IEMSis, which is 33–97-fold higher than that of the one without HPASi (IEM). The addition of HPASi also endows IEMSis good shape memory properties, and the shape fixity and shape recovery ratios of them are 97.5–97.6 and 91.4–93.7%, respectively. At the same time, IEMSis can undergo a stress relaxation process by dynamic exchanges of imine bonds under relatively mild conditions without a catalyst to acquire an ability of permanent shape reconfiguration. The shape retention ratio of IEMSi3 is 84.3%. In addition, the 4D-printed structures displayed here indicate that these 4D printing systems have a myriad of potential applications including aerospace structures, soft robotic grippers, smart electron switches, and intelligent packaging, while the reconfigurability shown by IEMSi3 will expand the scope of application fields of 4D printing materials.