3D-Printable Room Temperature Phosphorescence Polymer Materials with On-Demand Modulation for Modulus Visualization and Anticounterfeiting Applications

Zhen Li, Chuanzhen Zhang, Wenhuan Huang, Chenhui Cui, Kexiang Chen, Zhiyuan He, Ting Xu, Haoqing Teng, Zhishen Ge, Xiaoqing Ming and Yanfeng Zhang*, 
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Abstract

Conventional room temperature phosphorescence (RTP) polymer materials lack a dynamic structural change mechanism for on-demand phosphorescence emission, limiting their application in specific scenarios, such as smart devices. However, the development of RTP polymer materials with an on-demand emission capability is highly attractive yet rather challenging. Herein, we report a novel RTP polymer material that doped purely organic chromophores into a polymer network with numerous free hydroxyl side chains. This unique polymer material can be 3D printed with RTP activated through thermal-triggered nonequilibrium transesterification, where on-demand phosphorescence emission is achieved because of the increased cross-linking degrees such that the thermal motion of chromophores is effectively restricted. As a result, ultralong RTP emission is successfully observed due to enhanced stiffness in the polymer network. Importantly, the modulus changes of the polymer during nonequilibrium transesterification are intuitively visualized based on the intensity of phosphorescence emission. Through liquid crystal display (LCD) 3D printing, complex shaped and multimaterial structured objects are demonstrated, targeting the information encryption of printed objects and on-demand regional emission of multicolored phosphorescence. This study would provide an avenue to control RTP with on-demand emission and contributes to the field of anticounterfeiting and detection applications for intelligent RTP materials.

Abstract Image

用于模量可视化和防伪应用的可按需调制的 3D 打印室温磷光聚合物材料
传统的室温磷光(RTP)聚合物材料缺乏按需发射磷光的动态结构变化机制,这限制了它们在智能设备等特定场景中的应用。然而,开发具有按需发射能力的 RTP 聚合物材料极具吸引力,但也颇具挑战性。在此,我们报告了一种新型 RTP 聚合物材料,该材料将纯有机发色团掺杂到具有大量游离羟基侧链的聚合物网络中。这种独特的聚合物材料可通过热触发非平衡酯交换反应激活 RTP 进行 3D 打印,由于交联度提高,发色团的热运动受到有效限制,因此可实现按需磷光发射。因此,由于聚合物网络的刚性增强,成功观测到了超长的 RTP 发射。重要的是,根据磷光发射的强度,可以直观地观察到聚合物在非平衡酯交换过程中的模量变化。通过液晶显示器(LCD)三维打印,展示了复杂形状和多材料结构的物体,针对打印物体的信息加密和按需区域发射多色磷光。这项研究将为按需发射控制 RTP 提供一种途径,并有助于智能 RTP 材料的防伪和检测应用领域。
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