Dynamic imine bonds based shape memory polymers with permanent shape reconfigurability for 4D printing.

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 crosslinked (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 methacrylate monomer with aldehyde group (2-(methacryloyloxy)ethyl 4-formylbenzoate, MEFB) and hyperbranched crosslinker (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 are 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 ratio and shape recovery ratio of them are 97.5-97.6 % and 91.4-93.7 %, respectively. At the same time, IEMSis can undergo stress relaxation process by dynamic exchanges of imine bonds under relatively mild conditions without catalyst, thus 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 and smart electron switches, while the reconfigurability shown by IEMSi3 will expand the scope of application fields of 4D printing materials.

[1]  Ning Zheng,et al.  Healable, Reconfigurable, Reprocessable Thermoset Shape Memory Polymer with Highly Tunable Topological Rearrangement Kinetics. , 2017, ACS applied materials & interfaces.

[2]  Lang Xia,et al.  Stereolithographic 4D Bioprinting of Multiresponsive Architectures for Neural Engineering , 2018, Advanced biosystems.

[3]  Jiangtao Wu,et al.  3D Printing of Highly Stretchable, Shape-Memory, and Self-Healing Elastomer toward Novel 4D Printing. , 2018, ACS applied materials & interfaces.

[4]  Tao Xie,et al.  4D Printing: History and Recent Progress , 2018, Chinese Journal of Polymer Science.

[5]  Yue Zhao,et al.  Controlled 3D Shape Transformation Activated by Room Temperature Stretching and Release of Flat Polymer Sheet. , 2019, ACS applied materials & interfaces.

[6]  Tao Xie,et al.  Dynamic Covalent Polymer Networks: from Old Chemistry to Modern Day Innovations , 2017, Advanced materials.

[7]  Wei Huang,et al.  4D printing of shape memory polyurethane via stereolithography , 2018 .

[8]  L. Leibler,et al.  Vinylogous Urethane Vitrimers , 2015 .

[9]  Tuan Liu,et al.  Eugenol-Derived Biobased Epoxy: Shape Memory, Repairing, and Recyclability , 2017 .

[10]  Jing Bai,et al.  Dynamically Cross-linked Elastomer Hybrids with Light-Induced Rapid and Efficient Self-Healing Ability and Reprogrammable Shape Memory Behavior. , 2017, ACS applied materials & interfaces.

[11]  Yen Wei,et al.  Solvent-assisted programming of flat polymer sheets into reconfigurable and self-healing 3D structures , 2018, Nature Communications.

[12]  Guogao Zhang,et al.  Exploring Dynamic Equilibrium of Diels-Alder Reaction for Solid State Plasticity in Remoldable Shape Memory Polymer Network. , 2016, ACS macro letters.

[13]  Yanju Liu,et al.  Direct-Write Fabrication of 4D Active Shape-Changing Structures Based on a Shape Memory Polymer and Its Nanocomposite. , 2017, ACS applied materials & interfaces.

[14]  Zuming Hu,et al.  Bio-based epoxy vitrimers: Reprocessibility, controllable shape memory, and degradability , 2017 .

[15]  C. Yan,et al.  Four-dimensional printing of a novel acrylate-based shape memory polymer using digital light processing , 2019, Materials & Design.

[16]  Wei Huang,et al.  Three-Dimensional Printing of Shape Memory Composites with Epoxy-Acrylate Hybrid Photopolymer. , 2017, ACS applied materials & interfaces.

[17]  Lijie Sun,et al.  A Single Integrated 3D‐Printing Process Customizes Elastic and Sustainable Triboelectric Nanogenerators for Wearable Electronics , 2018, Advanced Functional Materials.

[18]  Tao Xie,et al.  Synergetic Chemical and Physical Programming for Reversible Shape Memory Effect in a Dynamic Covalent Network with Two Crystalline Phases. , 2019, ACS macro letters.

[19]  Zhong Zhang,et al.  Engineering Surface Patterns with Shape Memory Polymers: Multiple Design Dimensions for Diverse and Hierarchical Structures. , 2018, ACS applied materials & interfaces.

[20]  Qian Zhao,et al.  Catalyst-Free Thermoset Polyurethane with Permanent Shape Reconfigurability and Highly Tunable Triple-Shape Memory Performance. , 2017, ACS macro letters.

[21]  Lang Xia,et al.  4D printing of polymeric materials for tissue and organ regeneration. , 2017, Materials today.

[22]  A. Gu,et al.  Water-Phase Synthesis of a Biobased Allyl Compound for Building UV-Curable Flexible Thiol–Ene Polymer Networks with High Mechanical Strength and Transparency , 2018 .

[23]  Wei Zhu,et al.  4D printing smart biomedical scaffolds with novel soybean oil epoxidized acrylate , 2016, Scientific Reports.

[24]  Joshua M. Sadler,et al.  Preparation and Characterization of Highly Bio‐Based Epoxy Amine Thermosets Derived from Lignocellulosics , 2017 .

[25]  Martin L. Dunn,et al.  Advances in 4D Printing: Materials and Applications , 2018, Advanced Functional Materials.

[26]  Martin L. Dunn,et al.  Active origami by 4D printing , 2014 .

[27]  Pei-Chen Su,et al.  4D printing of high performance shape memory polymer using stereolithography , 2017 .

[28]  Jun Ni,et al.  A review of 4D printing , 2017 .

[29]  Ning Zheng,et al.  Thermoset Shape-Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation. , 2016, Angewandte Chemie.

[30]  Jizhou Song,et al.  Ultrafast Digital Printing toward 4D Shape Changing Materials , 2017, Advanced materials.

[31]  M. Layani,et al.  3D Printing of Shape Memory Polymers for Flexible Electronic Devices , 2016, Advanced materials.

[32]  Liqun Zhang,et al.  Malleable, Mechanically Strong, and Adaptive Elastomers Enabled by Interfacial Exchangeable Bonds , 2017 .

[33]  Yinzhen Pan,et al.  Reconfigurable and Reprocessable Thermoset Shape Memory Polymer with Synergetic Triple Dynamic Covalent Bonds. , 2018, Macromolecular rapid communications.

[34]  Shlomo Magdassi,et al.  Novel Materials for 3D Printing by Photopolymerization , 2018, Advanced materials.

[35]  Qi Ge,et al.  Active materials by four-dimension printing , 2013 .

[36]  Tao Xie,et al.  Shape memory polymer network with thermally distinct elasticity and plasticity , 2016, Science Advances.

[37]  M. Rong,et al.  Polymer engineering based on reversible covalent chemistry: A promising innovative pathway towards new materials and new functionalities , 2018 .

[38]  Junwei Gu,et al.  Tunable and Processable Shape-Memory Materials Based on Solvent-Free, Catalyst-Free Polycondensation between Formaldehyde and Diamine at Room Temperature. , 2019, ACS macro letters.

[39]  Daining Fang,et al.  Grayscale digital light processing 3D printing for highly functionally graded materials , 2019, Science Advances.

[40]  Dongxu Ke,et al.  Additive manufacturing of biomaterials. , 2018, Progress in materials science.

[41]  Z. Guan,et al.  Recyclable, Strong, and Highly Malleable Thermosets Based on Boroxine Networks. , 2018, Journal of the American Chemical Society.

[42]  Yanju Liu,et al.  Direct 3D Printing of Hybrid Nanofibers-based Nanocomposites for Highly Conductive and Shape Memory Applications. , 2019, ACS applied materials & interfaces.

[43]  Martin L. Dunn,et al.  Reprocessable thermosets for sustainable three-dimensional printing , 2018, Nature Communications.

[44]  Shiping Zhu,et al.  Reversible Shape Memory Polymer from Semicrystalline Poly(ethylene-co-vinyl acetate) with Dynamic Covalent Polymer Networks , 2018, Macromolecules.

[45]  Thomas J. Wallin,et al.  3D printing of soft robotic systems , 2018, Nature Reviews Materials.

[46]  C. R. Nair,et al.  Effect of phenol end functional switching segments on the shape memory properties of epoxy‐cyanate ester system , 2014 .

[47]  H. Qi,et al.  Recent progress in shape memory polymer: New behavior, enabling materials, and mechanistic understanding , 2015 .

[48]  N. Ning,et al.  Photothermal-Induced Self-Healable and Reconfigurable Shape Memory Bio-Based Elastomer with Recyclable Ability. , 2018, ACS applied materials & interfaces.

[49]  Yanju Liu,et al.  Shape-memory polymers and their composites: Stimulus methods and applications , 2011 .

[50]  Cedric P. Ambulo,et al.  Four-dimensional Printing of Liquid Crystal Elastomers. , 2017, ACS applied materials & interfaces.

[51]  Zhuangjian Liu,et al.  Self-Healing Four-Dimensional Printing with an Ultraviolet Curable Double-Network Shape Memory Polymer System. , 2019, ACS applied materials & interfaces.

[52]  Qihua Wang,et al.  Dual-Triggered and Thermally Reconfigurable Shape Memory Graphene-Vitrimer Composites. , 2016, ACS applied materials & interfaces.

[53]  Amir Hosein Sakhaei,et al.  Multimaterial 4D Printing with Tailorable Shape Memory Polymers , 2016, Scientific Reports.

[54]  R. Mülhaupt,et al.  Polymers for 3D Printing and Customized Additive Manufacturing , 2017, Chemical reviews.