Park Jihye, Kim Ahyun, Kim Byeong-Su
Department of Chemistry, Yonsei University, Seoul, 03722, Republic of Korea.
Nat Commun. 2023 Sep 20;14(1):5855. doi: 10.1038/s41467-023-41576-0.
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.
尽管机械化学聚合领域最近取得了进展，但要理解球磨聚合过程中独特的机械化学反应性仍需要进行大量研究。在此，采用固态阴离子开环聚合从各种功能性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。通过核磁共振（NMR）、凝胶渗透色谱（GPC）和基质辅助激光解吸电离飞行时间质谱（MALDI-ToF）分析对所需聚醚的可控合成进行了表征。有趣的是，与溶液聚合中观察到的情况形成鲜明对比的是，体积较大的单体在固态中表现出更快的转化率。特别是，观察到球磨聚合的转化率与功能性环氧化物单体的熔点之间存在密切的线性相关性，表明熔点是机械化学聚合反应性的关键预测指标。这项研究为机械化学聚合的高效设计和理解提供了见解。
