Radical ring‐opening polymerization (rROP) of cyclic ketene acetals (CKAs) combines the advantages of both ring‐opening polymerization and radical polymerization thereby allowing the robust production of polyesters coupled with the mild polymerization conditions of a radical process. rROP was recently rejuvenated by the possibility to copolymerize CKAs with classic vinyl monomers leading to the insertion of cleavable functionality into a vinyl‐based copolymer backbone and thus imparting (bio)degradability. Such materials are suitable for a large scope of applications, particularly within the biomedical field. The competition between the ring‐opening and ring‐retaining propagation routes is a major complication in the development of efficient CKA monomers, ultimately leading to the use of only four monomers that are known to completely ring‐open under all experimental conditions. In this article we investigate the radical ring‐opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict in silico the ring‐opening ability of CKA monomers.

中文翻译：

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通过自由基途径的聚酯：合理的循环乙烯酮缩醛效率。

环状烯酮缩醛（CKA）的自由基开环聚合（rROP）结合了开环聚合和自由基聚合的优点，从而使聚酯的生产稳健，同时自由基工艺的聚合条件温和。rROP最近通过将CKA与经典的乙烯基单体共聚的可能性而焕发出新的活力，从而导致可裂解的官能团插入乙烯基共聚物的主链中，从而赋予（生物）降解性。这样的材料适合于大范围的应用，特别是在生物医学领域内。开环和固环传播途径之间的竞争是开发高效CKA单体的主要复杂因素，最终导致仅使用在所有实验条件下完全开环的四种单体。在本文中，我们研究了模型CKA单体的自由基开环聚合反应，并通过DFT计算和使用PREDICI软件进行的动力学建模的结合证明，我们现在能够在计算机上预测CKA单体的开环能力。