Huang Xianmei, Peng Shuqiang, Zheng Longhui, Zhuo Dongxian, Wu Lixin, Weng Zixiang
CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Adv Mater. 2023 Dec;35(49):e2304430. doi: 10.1002/adma.202304430. Epub 2023 Nov 5.
Elastomers prepared via vat photopolymerizationus ually exhibit unsatisfied mechanical properties owing to their insufficient growth of molecular weight upon UV exposure. Increasing the weight ratio of oligomer in the resin system is an effective approach to enhance the mechanical properties, yet the viscosity of the UV-curable resin increases dramatically; this hinders its printing. In this study, a linear scan-based vat photopolymerization (LSVP) system which can print high-viscosity resins is implemented to 3D print the oligomer-dominated UV-curable resin via a dual-curing mechanism. A polyurethane methacrylate blocking oligomer is first synthesized and then mixed with a commercialized bifunctional oligomer, photoinitiator, and primary amine as a chain extender to prepare high-viscosity UV-curable resin for the LSVP system. The deblocked isocyanate is further crosslinked with a chain extender via thermal treatment to construct a highly entangled polymer chain network. The optimal thermal treatment parameters are investigated, and the resilience of the 3D-printed elastomer is evaluated through continuous tensile loading and unloading tests. Subsequently, complex structured elastomers are printed, exhibiting favorable mechanical durability without defects. The results obtained from this work will provide a reference for preparing elastomeric devices with excellent physical properties and expand the application scope of vat photopolymerization to new fields.
通过光固化3D打印制备的弹性体通常由于在紫外线照射下分子量增长不足而表现出不理想的机械性能。增加树脂体系中低聚物的重量比是提高机械性能的有效方法,但可紫外光固化树脂的粘度会急剧增加,这阻碍了其打印。在本研究中,采用一种基于线性扫描的光固化3D打印(LSVP)系统来3D打印高粘度树脂,该系统通过双重固化机制打印以低聚物为主的可紫外光固化树脂。首先合成一种聚氨酯甲基丙烯酸酯封端低聚物,然后将其与商业化的双官能低聚物、光引发剂和作为扩链剂的伯胺混合,以制备用于LSVP系统的高粘度可紫外光固化树脂。解封的异氰酸酯通过热处理进一步与扩链剂交联,以构建高度缠结的聚合物链网络。研究了最佳热处理参数,并通过连续拉伸加载和卸载试验评估了3D打印弹性体的回弹性。随后,打印出复杂结构的弹性体,其表现出良好的机械耐久性且无缺陷。本工作所得结果将为制备具有优异物理性能的弹性体器件提供参考,并将光固化3D打印的应用范围扩展到新领域。