Kwangwook Ko, Piper L. MacNicol, Mingming Zhu, Lei Zhang, Saifudin M. Abubakar and Jeremiah A. Johnson*,
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Guided by this insight, we establish predictive design criteria and introduce <b>Me</b><sub><b>4</b></sub><b>Si</b><sub><b>2</b></sub><b>O9</b>, a CC that exhibits near-ideal room temperature copolymerization with a broad range of norbornene-based (macro)monomers. <b>Me</b><sub><b>4</b></sub><b>Si</b><sub><b>2</b></sub><b>O9</b> 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.</p><p >A novel predictive workflow and entropy-maximizing design enabled the development of a cost-effective cleavable comonomer─<b>Me</b><sub><b>4</b></sub><b>Si</b><sub><b>2</b></sub><b>O9</b>─that uniformly embeds deconstructable bonds in ROMP-derived polymers.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 8","pages":"1408–1416"},"PeriodicalIF":10.4000,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscentsci.5c00521","citationCount":"0","resultStr":"{\"title\":\"Entropy Drives the Predictive Discovery of an Optimal Cleavable Comonomer for ROMP\",\"authors\":\"Kwangwook Ko, Piper L. MacNicol, Mingming Zhu, Lei Zhang, Saifudin M. Abubakar and Jeremiah A. Johnson*, \",\"doi\":\"10.1021/acscentsci.5c00521\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >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 <b>Me</b><sub><b>4</b></sub><b>Si</b><sub><b>2</b></sub><b>O9</b>, a CC that exhibits near-ideal room temperature copolymerization with a broad range of norbornene-based (macro)monomers. <b>Me</b><sub><b>4</b></sub><b>Si</b><sub><b>2</b></sub><b>O9</b> is significantly less expensive than leading silyl ether-based CCs and enables uniform incorporation of cleavable linkages into polymer backbones at low loadings. 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Entropy Drives the Predictive Discovery of an Optimal Cleavable Comonomer for ROMP
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.
A novel predictive workflow and entropy-maximizing design enabled the development of a cost-effective cleavable comonomer─Me4Si2O9─that uniformly embeds deconstructable bonds in ROMP-derived polymers.
期刊介绍:
ACS Central Science publishes significant primary reports on research in chemistry and allied fields where chemical approaches are pivotal. As the first fully open-access journal by the American Chemical Society, it covers compelling and important contributions to the broad chemistry and scientific community. "Central science," a term popularized nearly 40 years ago, emphasizes chemistry's central role in connecting physical and life sciences, and fundamental sciences with applied disciplines like medicine and engineering. The journal focuses on exceptional quality articles, addressing advances in fundamental chemistry and interdisciplinary research.