近日，一个由美国斯坦福大学Noah Z. Burns领导的合作小组通过机械力化学合成了一种难制备的含氟聚乙炔。2020年12月22日出版的《自然·化学》发表了这项成果。

研究人员通过高分子机械力化学合成了一种含氟聚乙炔，这是一种长久以来梦寐以求的空气中稳定的聚乙炔，但传统手段很难合成它。研究人员通过四步化学反应合成了克级的单体，其中包括通过一个奇异的光化学串联反应快速掺入氟原子，该反应的机理和特殊的手性选择性是通过计算得知的。然后，在聚合后，通过超声力活化生成了一种金色的半导体含氟高分子。这项研究表明高分子机械力化学是一种在制备级水平上获得新材料的有价值的合成工具。

据介绍，传统意义上的高分子机械力化学主要研究机械力对高分子骨架中的化学键的作用，以合成力响应材料。然而，通过对聚合物进行化学转化，高分子机械力化学在规模化合成其他方法无法合成的高分子材料方面的应用潜力仍有待挖掘。

附：英文原文

Title: Mechanochemical synthesis of an elusive fluorinated polyacetylene

Author: Benjamin R. Boswell, Carl M. F. Mansson, Jordan M. Cox, Zexin Jin, Joseph A. H. Romaniuk, Kurt P. Lindquist, Lynette Cegelski, Yan Xia, Steven A. Lopez, Noah Z. Burns

Issue&Volume: 2020-12-22

Abstract: Polymer mechanochemistry has traditionally been employed to study the effects of mechanical force on chemical bonds within a polymer backbone or to generate force-responsive materials. It is under-exploited for the scalable synthesis of wholly new materials by chemically transforming the polymers, especially products inaccessible by other means. Here we utilize polymer mechanochemistry to synthesize a fluorinated polyacetylene, a long-sought-after air-stable polyacetylene that has eluded synthesis by conventional means. We construct the monomer in four chemical steps on gram scale, which involves a rapid incorporation of fluorine atoms in an exotic photochemical cascade whose mechanism and exquisite stereoselectivity were informed by computation. After polymerization, force activation by ultrasonication produces a gold-coloured, semiconducting fluoropolymer. This work demonstrates that polymer mechanochemistry is a valuable synthetic tool for accessing materials on a preparative scale.

DOI: 10.1038/s41557-020-00608-8

Source: https://www.nature.com/articles/s41557-020-00608-8