Zhang Yuwen, Lo Bocchiaro Alessio, Hu Xiaolei, Pavon Carlos, Pezzato Cristian, Matyjaszewski Krzysztof, Lorandi Francesca, Benetti Edmondo M
Laboratory for Macromolecular and Organic Chemistry, Department of Chemical Sciences, University of Padova, Via Marzolo 1, Padova 35131, Italy.
Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.
ACS Appl Mater Interfaces. 2025 Jul 2;17(26):38773-38782. doi: 10.1021/acsami.5c08584. Epub 2025 Jun 18.
The translation of polymer brushes into technologically relevant coatings hinges on the development of scalable and robust fabrication strategies that are tolerant of environmental conditions. Surface-initiated photoinduced atom transfer radical polymerization (SI-photoATRP) has emerged as a powerful tool for synthesizing functional brushes with precise control over their architectural parameters. However, traditional SI-photoATRP requires high-energy light and confined setups to mitigate oxygen inhibition within nondeoxygenated mixtures, limiting substrate versatility and process scalability. Herein, we report a red-light-driven SI-photoATRP process enabled by a catalytic system composed of methylene blue (MB) and a Cu-based ATRP catalyst, which achieves efficient polymer brush growth under fully open-air conditions. Systematic variation of reaction parameters─including light intensity, composition of the catalytic system, and solvent─enabled rapid growth of compositionally different brushes with high and tunable thickness. The deep penetration capability of red light was exploited to decorate microporous three-dimensional materials with polymer brushes. Spatially defined brush growth was demonstrated by shifting the wavelength of light irradiation, alternatively stimulating surface-initiated polymerization in the outer volumes of the support or uniformly across the entire microporous material.
将聚合物刷转化为具有技术相关性的涂层，取决于能否开发出可扩展且稳健的制造策略，这些策略要能耐受环境条件。表面引发的光诱导原子转移自由基聚合（SI-光引发原子转移自由基聚合）已成为一种强大的工具，可用于合成功能刷，并能精确控制其结构参数。然而，传统的SI-光引发原子转移自由基聚合需要高能光和受限的装置，以减轻未脱氧混合物中的氧抑制作用，这限制了底物的通用性和工艺的可扩展性。在此，我们报道了一种由亚甲蓝（MB）和铜基原子转移自由基聚合催化剂组成的催化体系实现的红光驱动的SI-光引发原子转移自由基聚合过程，该过程在完全露天条件下实现了高效的聚合物刷生长。通过系统改变反应参数——包括光强度、催化体系组成和溶剂——能够快速生长具有不同组成且厚度高且可调的刷子。利用红光的深穿透能力，用聚合物刷对微孔三维材料进行修饰。通过改变光照射波长，交替刺激载体外部体积或整个微孔材料上的表面引发聚合，证明了空间定义的刷生长。
