Department of Chemistry, University of Fribourg, Chemin du Musée 9, CH-1700 Fribourg, Switzerland.
ACS Macro Lett. 2022 Jun 21;11(6):813-817. doi: 10.1021/acsmacrolett.2c00234. Epub 2022 Jun 8.
Heterotelechelic polymers are an important class of materials finding applications in bioconjugation, imaging, sensing, and synthesis of organic/inorganic hybrid systems with interesting features. However, the synthesis of such polymers is challenging. Here, we report a mechanistically unique and most efficient method based on a single functionalization agent to prepare heterotelechelic polymers by a ring-opening metathesis polymerization. Different functionalization agents can be synthesized in one simple step from inexpensive commercial starting materials. The functionalization agents initially generate a functional initiator from commercial Grubbs' first-generation ruthenium benzylidene catalyst. During this process, a functional dihydrofuran derivative is produced. After functional initiation and propagation of a suitable monomer, the dihydrofuran derivative functionally terminates the polymerization yielding a primary alcohol-terminated heterotelechelic polymer. Molecular weight control is achieved by varying the ratio between monomer and Grubbs' first-generation catalyst. This method may emerge as a popular choice to prepare heterotelechelic polymers due to its simplicity and efficiency.
杂臂聚合物是一类重要的材料，在生物缀合、成像、传感以及具有有趣特性的有机/无机杂化系统的合成中都有应用。然而，这类聚合物的合成具有挑战性。在这里，我们报告了一种基于单官能团试剂的机械独特且最高效的方法，通过开环复分解聚合制备杂臂聚合物。不同的官能团试剂可以通过从廉价的商业起始原料一步简单合成得到。官能团试剂最初从商业的 Grubbs 第一代钌苄叉催化剂生成一个官能团引发剂。在这个过程中，产生了一个官能化的二氢呋喃衍生物。在合适的单体进行官能化引发和聚合后，二氢呋喃衍生物官能化终止聚合，得到伯醇封端的杂臂聚合物。通过改变单体和第一代 Grubbs 催化剂的比例可以实现分子量控制。由于其简单高效，这种方法可能成为制备杂臂聚合物的一种流行选择。
