Entropy Drives the Predictive Discovery of an Optimal Cleavable Comonomer for ROMP
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entropy-drives-the-predictive-discovery-of-an-optimal-cleavable-comonomer-for-romp.pdf
Description
Published version
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3.96 MB
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Author(s)
Ko, Kwangwook
MacNicol, Piper L
Zhu, Mingming
Zhang, Lei
Abubakar, Saifudin M
Johnson, Jeremiah A
Date Issued
July 23, 2025
Journal
ACS Central Science
Publisher
American Chemical Society
Citation
Kwangwook Ko, Piper L. MacNicol, Mingming Zhu, Lei Zhang, Saifudin M. Abubakar, Jeremiah A. Johnson; Entropy Drives the Predictive Discovery of an Optimal Cleavable Comonomer for ROMP. ACS Cent. Sci. 27 August 2025; 11 (8): 1408–1416.
Version
Final published version
Abstract
Ring-opening metathesis polymerization (ROMP) of norbornene derivatives enables access to polymeric materials for applications ranging from targeted drug delivery to high-performance thermosets; however, the carbon–carbon backbones of ROMP-derived poly(norbornenes) resist deconstruction under mild, selective conditions. Cleavable comonomers (CCs) have been introduced to address this limitation, yet their implementation has been hindered by prohibitive costs and/or suboptimal reactivity. Moreover, the discovery of existing CCs has been largely empirical, lacking clear design principles. Here, we identify the entropy of ring-opening as one of the key determinants of ROMP copolymerization behavior of the best-performing CCs reported to date. Guided by this insight, we establish predictive design criteria and introduce Me4Si2O9, a CC that exhibits near-ideal room temperature copolymerization with a broad range of norbornene-based (macro)monomers. Me4Si2O9 is significantly less expensive than leading silyl ether-based CCs and enables uniform incorporation of cleavable linkages into polymer backbones at low loadings. Beyond delivering a cost-effective and high-performance CC, this work provides fundamental insights into ROMP copolymerization that will enable predictive CC development and expand the functional scope of deconstructable polymeric materials.
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DOI of Published Version
https://doi.org/10.1021/acscentsci.5c00521
