Photoinduced polymerization techniques have gathered significant attention due to their mild conditions, spatiotemporal control, and simple setup. In addition to homogeneous media, efforts have been made to implement photopolymerization in emulsions as a practical and greener process. However, previous photoinduced reversible deactivation radical polymerization (RDRP) in heterogeneous media has relied on short-wavelength lights, which have limited penetration depth, resulting in slow polymerization and relatively poor control. In this study, we demonstrate the first example of a highly efficient photoinduced miniemulsion ATRP in the open air driven by red or near-infrared (NIR) light. This was facilitated by the utilization of a water-soluble photocatalyst, methylene blue (MB⁺). Irradiation by red/NIR light allowed for efficient excitation of MB⁺ and subsequent photoreduction of the ATRP deactivator in the presence of water-soluble electron donors to initiate and mediate the polymerization process. The NIR light-driven miniemulsion photoATRP provided a successful synthesis of polymers with low dispersity (1.09 ≤ Đ ≤ 1.29) and quantitative conversion within an hour. This study further explored the impact of light penetration on polymerization kinetics in reactors of varying sizes and a large-scale reaction (250 mL), highlighting the advantages of longer-wavelength light, particularly NIR light, for large-scale polymerization in dispersed media owing to its superior penetration. This work opens new avenues for robust emulsion photopolymerization techniques, offering a greener and more practical approach with improved control and efficiency.

中文翻译：

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由红光和近红外光驱动的稳健细乳液 PhotoATRP

光诱导聚合技术由于其条件温和、时空控制和简单的设置而引起了极大的关注。除了均质介质之外，人们还努力将乳液中的光聚合作为一种实用且更环保的工艺。然而，以往非均相介质中的光诱导可逆失活自由基聚合（RDRP）依赖于短波长光，其穿透深度有限，导致聚合速度缓慢且控制性相对较差。在这项研究中，我们展示了第一个在露天由红光或近红外 (NIR) 光驱动的高效光诱导细乳液 ATRP 的例子。这是通过使用水溶性光催化剂亚甲蓝（MB ⁺）来促进的。红光/近红外光照射可以有效激发 MB ⁺并随后在水溶性电子供体存在下光还原 ATRP 失活剂，从而引发和介导聚合过程。近红外光驱动的细乳液 photoATRP 成功合成了低分散度 (1.09 ≤ Đ ≤ 1.29) 的聚合物，并在一小时内实现了定量转化。本研究进一步探讨了不同尺寸反应器和大规模反应（250 mL）中光穿透对聚合动力学的影响，强调了较长波长的光，特别是近红外光对于分散介质中大规模聚合的优势以其卓越的渗透力。这项工作为稳健的乳液光聚合技术开辟了新途径，提供了一种更环保、更实用的方法，并提高了控制和效率。