Despite recent advancements in mechanochemical polymerization, understanding the unique mechanochemical reactivity during the ball milling polymerization process still requires extensive investigations. Herein, solid-state anionic ring-opening polymerization is used to synthesize polyethers from various functional epoxide monomers. The critical parameters of the monomers are investigated to elucidate the unique reactivity of ball milling polymerization. The controllable syntheses of the desired polyethers are characterized via NMR, GPC, and MALDI-ToF analyses. Interestingly, bulky monomers exhibit faster conversions in the solid-state in clear contrast to that observed for solution polymerization. Particularly, a close linear correlation is observed between the conversion of the ball milling polymerization and melting point of the functional epoxide monomers, indicating melting point as a critical predictor of mechanochemical polymerization reactivity. This study provides insights into the efficient design and understanding of mechanochemical polymerization.

尽管机械化学聚合最近取得了进展，但了解球磨聚合过程中独特的机械化学反应性仍然需要广泛的研究。在此，固态阴离子开环聚合用于从各种官能环氧化物单体合成聚醚。研究了单体的关键参数，以阐明球磨聚合的独特反应性。通过 NMR、GPC 和 MALDI-ToF 分析对所需聚醚的可控合成进行了表征。有趣的是，大体积单体在固态下表现出更快的转化，这与溶液聚合中观察到的情况形成鲜明对比。特别是，在球磨聚合的转化率和官能环氧化物单体的熔点之间观察到密切的线性相关性，表明熔点是机械化学聚合反应性的关键预测因子。这项研究提供了对机械化学聚合的有效设计和理解的见解。