Photopolymers have been optimized as protective and decorative coating materials for decades. However, with the rise of additive manufacturing technologies, vat photopolymerization has unlocked the use of photopolymers for three-dimensional objects with new material requirements. Thus, the originally highly cross-linked, amorphous architecture of photopolymers cannot match the expectations for modern materials anymore, revealing the largely unanswered question of how diverse properties can be achieved in photopolymers. Herein, we review how microstructural features in soft matter materials should be designed and implemented to obtain high performance materials. We then translate these findings into chemical design suggestions for enhanced printable photopolymers. Based on this analysis, we have found microstructural heterogenization to be the most powerful tool to tune photopolymer performance. By combining the chemical toolbox for photopolymerization and the analytical toolbox for microstructural characterization, we examine current strategies for physical heterogenization (fillers, inkjet printing) and chemical heterogenization (semicrystalline polymers, block copolymers, interpenetrating networks, photopolymerization induced phase separation) of photopolymers and put them into a material scientific context to develop a roadmap for improving and diversifying photopolymers’ performance.

中文翻译：

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从不受监管的网络到设计的微观结构：在增材制造的光聚合物中引入不同长度尺度的异质性

数十年来，光聚合物一直被优化为保护性和装饰性涂层材料。然而，随着增材制造技术的兴起，还原光聚合解锁了光聚合物在三维物体中的应用，并提出了新的材料要求。因此，光聚合物最初的高度交联、无定形结构不再符合现代材料的期望，揭示了如何在光聚合物中实现多种性能这一在很大程度上尚未得到解答的问题。在此，我们回顾了如何设计和实现软物质材料的微观结构特征以获得高性能材料。然后，我们将这些发现转化为增强可印刷光聚合物的化学设计建议。基于此分析，我们发现微观结构异质化是调整光聚合物性能的最有力工具。通过结合用于光聚合的化学工具箱和用于微结构表征的分析工具箱，我们研究了光聚合物的物理异质化（填料、喷墨印刷）和化学异质化（半晶聚合物、嵌段共聚物、互穿网络、光聚合诱导相分离）的当前策略，并提出了将它们纳入材料科学背景，以制定改善光聚合物性能并使之多样化的路线图。