Darby D R, Greenlee A J, Bean R H, Fairchild D C, Rodriguez V C, Jansen A L, Gallegos S C, Ramirez S P, Moore J S, Leguizamon S C, Appelhans L N
Sandia National Laboratories, Albuquerque, NM, USA.
University of Illinois, Champaign, IL, USA.
Nat Commun. 2025 Jul 8;16(1):6291. doi: 10.1038/s41467-025-61484-9.
Frontal ring-opening metathesis polymerization (FROMP) is a promising energy-efficient approach to fabricate polymeric materials. Recent advances have demonstrated FROMP for diverse applications, including additive manufacturing, composites, and foams. However, the characteristic properties of the front are currently controlled primarily by varying the resin composition or the environmental conditions. In this work we present an approach to control FROMP of dicyclopentadiene (DCPD) using photochemical methods. A photobase generator is used to inhibit FROMP of DCPD with UV light while a photosensitizer and co-initiator are used to accelerate FROMP with blue light, enabling orthogonal active photocontrol of front velocity. In addition, photoinhibition-enabled lithographic patterning of frontal polymerizations is demonstrated. Frontal polymerizations are spatially controlled, redirected, and even split into diverging fronts. This work establishes a foundation for advanced control of frontal polymerizations, enabling innovation in traditional and additive manufacturing, as well as emerging processes like morphogenic manufacturing.
前沿开环易位聚合（FROMP）是一种很有前景的制造聚合物材料的节能方法。最近的进展表明FROMP可用于多种应用，包括增材制造、复合材料和泡沫材料。然而，目前前沿的特性主要通过改变树脂组成或环境条件来控制。在这项工作中，我们提出了一种使用光化学方法控制双环戊二烯（DCPD）的FROMP的方法。光碱发生器用于通过紫外光抑制DCPD的FROMP，而光敏剂和共引发剂用于通过蓝光加速FROMP，从而实现对前沿速度的正交主动光控制。此外，还展示了基于光抑制的前沿聚合光刻图案化。前沿聚合在空间上得到控制、重新定向，甚至分裂成发散的前沿。这项工作为前沿聚合的高级控制奠定了基础，能够在传统制造和增材制造以及形态发生制造等新兴工艺中实现创新。
