Living polymerizations of polar vinyl monomers have been successful for decades. However, they still suffer the following challenges: fast propagation, air-moisture tolerance, and negligible side reactions even at elevated temperatures. Here, we developed an unprecedented polymerization that overcomes these limitations using a Lewis pair catalyst. The anionic polymerization of dialkyl acrylamides proceeded in a living/controlled matter using Zn(OTf)₂/PPh₃ within a wide temperature range of 25–100 °C for short times (1–10 min) even under open-air conditions. The recovery and reuse of Zn(OTf)₂ without loss of polymerization activity were observed to be possible. The polymerization was retarded by excess Zn(OTf)₂, the additive methanol, and water, indicating equilibriums of the propagating species with them. The putative propagating zinc triflate-ate complex was tolerant to the protic additives and significantly selective for the propagation.

中文翻译：

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三氟磺酸锌/磷化氢 Lewis 对二烷基丙烯酰胺进行高耐受性活/受控阴离子聚合


几十年来，极性乙烯基单体的活性聚合已经取得了成功。然而，它们仍然面临以下挑战：快速繁殖、空气湿气耐受性以及即使在高温下也能忽略不计的副反应。在这里，我们开发了一种前所未有的聚合方法，使用 Lewis 对催化剂克服了这些限制。即使在露天条件下，在 25-100 °C 的宽温度范围内，使用 Zn（OTf）₂/PPh₃ 在活体/受控物质中进行二烷基丙烯酰胺的阴离子聚合也在短时间内（1-10 分钟）。观察到 Zn（OTf）₂ 的回收和再利用而不损失聚合活性是可能的。过量的 Zn（OTf）₂、添加剂甲醇和水阻碍了聚合反应，表明繁殖物质与它们处于平衡状态。推定的增殖三氟甲酸锌复合物对质子添加剂具有耐受性，并且对繁殖具有显著的选择性。