A facile method is reported for rapid, room‐temperature synthesis of block copolymers (BCP) of complex morphology and hence nontraditional spherical assembly. The use of solvated electrons generates radical anions on olefinic monomers, and with a felicitous choice of monomer pairs, this species will propagate bimechanistically (via radical and the anion) to form BCPs. Molecular weight of the obtained BCP range from M_w = 97 000–404 000 g mol⁻¹ (polydispersity index, PDI = 1.4–3.0) depending on monomer pairs. The composition of the blocks can be controlled by changing monomer ratio, with the caveat that yield is affected. Detailed characterization by 2D nuclear magnetic resonance spectroscopy, differential scanning calorimetry (DSC), and analysis of the mechanisms involved indicate the structure of obtained block copolymers to be at least a triblock with a complex central unit. Evaluating trends in the Hammett parameter segregates monomer pairs into “armed and disarmed” groups with respect to radical or anionic polymerization akin to oligosaccharides synthesis.

中文翻译：

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使用感应“解除武装”的单体对快速一步合成复杂的结构嵌段聚合物

据报道，一种简便的方法可以在室温下快速合成形态复杂的嵌段共聚物（BCP），从而实现非传统的球形组装。使用溶剂化电子的产生上的烯属单体自由基阴离子，并用单体对一个恰当的选择，这物种将bimechanistically传播（通过自由基，阴离子），以形成过境点。获得的BCP的分子量为M _w = 97 000–404 000 g mol ^-1（多分散指数，PDI = 1.4-3.0）取决于单体对。嵌段的组成可以通过改变单体比例来控制，但要注意的是，产率会受到影响。通过2D核磁共振波谱，差示扫描量热法（DSC）进行的详细表征以及所涉及机理的分析表明，所获得的嵌段共聚物的结构至少是具有复杂中心单元的三嵌段。对于类似于寡糖合成的自由基或阴离子聚合，评估Hammett参数的趋势会将单体对分为“武装和解除武装”基团。