Zeitler Sarah M, Chakma Progyateg, Golder Matthew R
Department of Chemistry, Molecular Engineering & Science Institute, University of Washington 36 Bagley Hall Seattle WA 98195 USA
Chem Sci. 2022 Mar 16;13(14):4131-4138. doi: 10.1039/d2sc00313a. eCollection 2022 Apr 6.
Mechanically-induced redox processes offer a promising alternative to more conventional thermal and photochemical synthetic methods. For macromolecule synthesis, current methods utilize sensitive transition metal additives and suffer from background reactivity. Alternative methodology will offer exquisite control over these stimuli-induced mechanoredox reactions to couple force with redox-driven chemical transformations. Herein, we present the iodonium-initiated free-radical polymerization of (meth)acrylate monomers under ultrasonic irradiation and ball-milling conditions. We explore the kinetic and structural consequences of these complementary mechanical inputs to access high molecular weight polymers. This methodology will undoubtedly find broad utility across stimuli-controlled polymerization reactions and adaptive material design.
机械诱导的氧化还原过程为更传统的热合成和光化学合成方法提供了一种有前景的替代方案。对于大分子合成，当前方法使用敏感的过渡金属添加剂且存在背景反应性问题。替代方法将能对这些刺激诱导的机械氧化还原反应进行精确控制，从而将力与氧化还原驱动的化学转化相结合。在此，我们展示了在超声辐照和球磨条件下碘鎓引发的（甲基）丙烯酸酯单体的自由基聚合反应。我们探究了这些互补机械输入对获得高分子量聚合物的动力学和结构影响。这种方法无疑将在刺激控制的聚合反应和自适应材料设计中具有广泛的应用。
