Ko Kwangwook, MacNicol Piper L, Zhu Mingming, Zhang Lei, Abubakar Saifudin M, Johnson Jeremiah A
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
ExxonMobil Asia Pacific Research and Development Co., Ltd., Shanghai 200241, China.
ACS Cent Sci. 2025 Jul 23;11(8):1408-1416. doi: 10.1021/acscentsci.5c00521. eCollection 2025 Aug 27.
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 , a CC that exhibits near-ideal room temperature copolymerization with a broad range of norbornene-based (macro)-monomers. 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.
降冰片烯衍生物的开环易位聚合（ROMP）能够制备出适用于从靶向药物递送至高性能热固性材料等各种应用的聚合物材料；然而，ROMP衍生的聚（降冰片烯）的碳-碳主链在温和的选择性条件下难以解构。为解决这一局限性，人们引入了可裂解共聚单体（CCs），但其应用受到高成本和/或次优反应活性的阻碍。此外，现有CCs的发现很大程度上是经验性的，缺乏明确的设计原则。在此，我们确定开环熵是迄今为止报道的性能最佳的CCs的ROMP共聚行为的关键决定因素之一。基于这一见解，我们建立了预测性设计标准，并引入了一种CC，它与多种基于降冰片烯的（大分子）单体表现出近乎理想的室温共聚性能。这种CC比领先的基于甲硅烷基醚的CCs便宜得多，并且能够在低负载量下将可裂解键均匀地引入聚合物主链。除了提供一种经济高效且高性能的CC外，这项工作还为ROMP共聚提供了基本见解，这将有助于进行预测性CC开发，并扩大可解构聚合物材料的功能范围。
