Cleavable Strand‐Fusing Cross‐Linkers as Additives for Chemically Deconstructable Thermosets with Preserved Thermomechanical Properties

Zhang, Shuyi; Xu, Zhenchuang; Husted, Keith E. L.; Lundberg, David J.; Brown, Christopher M.; Wang, Yuyan; Shieh, Peyton; Ko, Kwangwook; Moore, Jeffrey S.; Johnson, Jeremiah A.

doi:10.1002/ange.202500104

Cleavable Strand‐Fusing Cross‐Linkers as Additives for Chemically Deconstructable Thermosets with Preserved Thermomechanical Properties

Journal Article · Thu Mar 27 00:00:00 EDT 2025 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202500104· OSTI ID:2543100

Zhang, Shuyi ^[1]; Xu, Zhenchuang ^[2]; Husted, Keith E. L. ^[1]; Lundberg, David J. ^[3]; Brown, Christopher M. ^[1]; Wang, Yuyan ^[1]; Shieh, Peyton ^[1]; Ko, Kwangwook ^[1]; Moore, Jeffrey S. ^[2]; ^[1]

Department of Chemistry Massachusetts Institute of Technology Cambridge Massachusetts 02139 USA
Beckman Institute for Advanced Science and Technology University of Illinois at Urbana–Champaign Urbana Illinois 61801 USA, Department of Chemistry University of Illinois at Urbana–Champaign Urbana Illinois 61801 USA
Department of Chemical Engineering Massachusetts Institutes of Technology Cambridge Massachusetts 02139 USA

Abstract

Permanently cross‐linked polymer networks—thermosets—are often difficult to chemically deconstruct. The installation of cleavable bonds into the strands of thermosets using cleavable comonomers as additives can facilitate thermoset deconstruction without replacement of permanent cross‐links, but such monomers can lead to reduced thermomechanical properties and require high loadings to function effectively, motivating the design of new and optimal cleavable additives. Here, we introduce “strand‐fusing cross‐linkers” (SFCs), which fuse two network strands via a four‐way cleavable cross‐link. SFCs enable deconstruction of model polydicyclopentadiene (pDCPD) thermosets with as little as one‐fifth of the molar loading needed to achieve deconstruction using traditional cleavable comonomers. SFCs function under traditional oven curing as well as low‐energy frontal ring‐opening metathesis polymerization (FROMP) conditions and lead to improved thermomechanical properties, for example, glass transition temperatures, compared to prior cleavable comonomer designs. This work motivates the development of increasingly improved cleavable additives to enable thermoset deconstruction without compromising material performance.

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Sponsoring Organization:: USDOE

OSTI ID:: 2543100

Alternate ID(s):: OSTI ID: 2564523

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 19 Vol. 137; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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