Active light-controlled frontal ring-opening metathesis polymerization

Journal Article · Tue Jul 08 00:00:00 EDT 2025 · Nature Communications

DOI:https://doi.org/10.1038/s41467-025-61484-9· OSTI ID:2585532

Darby, Daniel Richard ^[1]; Greenlee, Andrew James ^[2]; Bean, Ren Harrison ^[1]; Fairchild, David Chase ^[1]; Rodriguez, Victoria Carolina ^[1]; Jansen, Annika Lindsey ^[1]; Gallegos, Shantae Christiana ^[1]; Ramirez, Salma P. ^[1]; Moore, J. S. ^[3]; Leguizamon, Samuel Carlos ^[1]; Appelhans, Leah N. ^[1]

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1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Univ. of Illinois at Urbana-Champaign, IL (United States)
3. Univ. of Illinois at Urbana-Champaign, IL (United States)

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.

• Research Organization: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Univ. of Illinois at Urbana-Champaign, IL (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
• Grant/Contract Number: NA0003525; SC0023457
• OSTI ID: 2585532
• Alternate ID(s): OSTI ID: 2583740
• Report Number(s): SAND--2025-10029J; 1782089
• Journal Information: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 16; ISSN 2041-1723
• Publisher: Nature Publishing Group
• Country of Publication: United States
• Language: English

Related Subjects

Polymer synthesis
Polymers