Aqueous electrochemical atom transfer radical polymerisation (eATRP) can be challenging due to deleterious side reactions leading to the loss of the ω-chain end, increased rates of activation (k_act) leading to higher [P_n˙], increased rates of termination, and the lability of the X–Cu^II/L bond to hydrolysis leading to poor control. Herein, we build on recent advances in eATRP methodology to develop a simplified current-controlled eATRP of acrylamides in water. The simplification arises from the use of commercial, standardised reaction hardware which enables the polymerisations to be performed in a 2-electrode, ‘plug-and-play’, undivided electrochemical cell configuration. Further simplification is afforded by the design of a single stepwise current profile (I_app vs. time) capable of mediating current-controlled eATRP of N-hydroethylacrylamide (HEAm). At room temperature, polymerisation of HEAm to target degrees of polymerisation (DP_n,th) of 20–100 proceeds with good control (Đ ≤ 1.50). Loss of control when targeting higher DP_n at room temperature is circumvented by lowering the reaction temperature (RT to 0 °C), increasing the stirring rate (400 rpm to 800 rpm) and increasing the catalyst concentration. Using the best conditions, a linear increase in M_n,SEC with DP_n (up to DP_n = 320) and low dispersity values (DP_n,th = 40–160; Đ = 1.26–1.38) were obtained. Furthermore, the current profile and reaction conditions can support the polymerisation of other primary and secondary acrylamides and the retention of the ω-Br chain end is exemplified by a short in situ chain extension. Overall, this represents further simplification of aqueous eATRP with respect to reaction set up and experimental parameters (single current profile) which has been employed to synthesise polyacrylamides with good efficiency and control.

中文翻译：

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丙烯酰胺在水中的电流控制“即插即用”电化学原子转移自由基聚合

水性电化学原子转移自由基聚合 (eATRP) 可能具有挑战性，因为有害的副反应会导致 ω 链末端的损失、活化率增加 ( k _act ) 会导致更高的 [P _n ˙]、终止率增加、和 X-Cu ^{II的不稳定性}/L 键与水解导致不良控制。在此，我们在 eATRP 方法学的最新进展的基础上开发了一种简化的电流控制的丙烯酰胺在水中的 eATRP。简化源于使用商业化、标准化的反应硬件，这使得聚合反应能够在 2 电极、“即插即用”、不可分割的电化学电池配置中进行。通过设计能够调节N-氢乙基丙烯酰胺(HEAm)的电流控制 eATRP 的单个逐步电流分布 ( I _app 与时间) 的设计进一步简化。在室温下，HEAm 聚合到 20-100 的目标聚合度 (DP _{n ,th} ) 可以很好地控制 ( Đ≤ 1.50)。通过降低反应温度（RT 至 0 °C）、增加搅拌速度（400 rpm 至 800 rpm）和增加催化剂浓度来避免在室温下以更高的 DP _n为目标时失去控制。使用最佳条件， M _n,SEC随 DP _n（高达 DP _n = 320）和低分散值（DP _{n ,th} = 40–160；Đ = 1.26–1.38）线性增加。此外，电流分布和反应条件可以支持其他伯和仲丙烯酰胺的聚合，并且 ω-Br 链端的保留可以通过原位短路来举例说明链条延伸。总体而言，这代表了水性 eATRP 在反应设置和实验参数（单电流曲线）方面的进一步简化，这些参数已用于以良好的效率和控制合成聚丙烯酰胺。