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.

聚合物机械化学传统上用于研究机械力对聚合物骨架内化学键的影响或生成力响应材料。通过对聚合物进行化学转化，特别是通过其他方式无法获得的产品，它在全新材料的可扩展合成方面尚未得到充分利用。在这里，我们利用聚合物机械化学合成氟化聚乙炔，这是一种备受追捧的空气稳定聚乙炔，传统方法无法合成。我们在克级的四个化学步骤中构建单体，其中包括将氟原子快速结合到奇异的光化学级联中，其机制和精细的立体选择性通过计算得到了信息。聚合后，通过超声波作用力活化产生金色，半导体含氟聚合物。这项工作表明，聚合物机械化学是一种有价值的合成工具，可用于制备规模的材料。