Red-Light-Activated Dual Photocatalytic ATRP of Methacrylates and Acrylates Enabled by Copper Phthalocyanines

IF 5.7 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2026-10-16 DOI:10.1021/acs.macromol.6c01816

Edina Rusen,Cristina Stavarache,Aurel Diacon,Alexandra Mocanu,Gabriela Toader,Oana Brincoveanu,Ana-Mihaela Gavrila,Livia Alexandra Dinu

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引用次数: 0

Abstract

Abstract Copper phthalocyanines (Pc) represent a promising yet underexplored class of low-cost and photostable dyes for visible-light-mediated polymerizations. In this study, we demonstrate that copper phthalocyanine (CuPc) and its derivatives efficiently mediate dual photocatalyst/copper atom transfer radical polymerization (PC/Cu-ATRP) of acrylates and methacrylates under red-light irradiation (λ = 628 nm). Using methyl acrylate (MA) as a model monomer, CuPc and its chlorinated derivative (CuPc-Cl) enable controlled polymerization in DMSO at ambient temperature, whereas the aminated analogue (CuPc-NH2) exhibits substantially lower activity. Kinetic analysis reveals apparent first-order behavior with respect to the monomer, with higher polymerization rates observed for CuPc compared to CuPc-Cl, consistent with differences in solubility. The resulting polymers display predictable molar mass evolution, low dispersity (Đ < 1.3), and good temporal control under intermittent irradiation. High chain-end fidelity is confirmed by successful chain extension, affording PMA-b-PMMA block copolymers. Molecular weight can be readily tuned by varying the monomer-to-initiator ratio. As a practical demonstration, CuPc was applied in the suspension polymerization of methyl methacrylate (MMA), yielding polymer particles (3–20 μm) incorporating the dye, as confirmed by optical microscopy and scanning electron microscopy (SEM). These findings establish copper phthalocyanines as efficient and accessible photocatalysts for red-light-driven controlled radical polymerization.

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酞菁铜催化甲基丙烯酸酯和丙烯酸酯的红光活化双光催化ATRP

摘要：酞菁铜（Pc）是一种有前途但尚未开发的低成本、光稳定性染料，可用于可见光介导的聚合。在本研究中，我们证明了酞菁铜（CuPc）及其衍生物在红光（λ = 628 nm）照射下有效地介导丙烯酸酯和甲基丙烯酸酯的双光催化剂/铜原子转移自由基聚合（PC/Cu-ATRP）。以丙烯酸甲酯（MA）为模型单体，CuPc及其氯化衍生物（cup - cl）可以在室温下在DMSO中进行可控聚合，而胺化类似物（cup - nh2）的活性则低得多。动力学分析表明，相对于单体而言，CuPc具有明显的一级行为，与cup - cl相比，CuPc的聚合速率更高，这与溶解度的差异一致。所得聚合物在间歇性辐照下表现出可预测的摩尔质量演化、低分散性（Đ < 1.3）和良好的时间控制性。成功的链延伸证实了高链端保真度，提供了PMA-b-PMMA嵌段共聚物。分子量可以很容易地调整通过改变单体与引发剂的比例。将CuPc应用于甲基丙烯酸甲酯（MMA）的悬浮聚合中，通过光学显微镜和扫描电子显微镜（SEM）的观察，得到了3 ~ 20 μm的含染料聚合物颗粒。这些发现证实了酞菁铜是红光驱动可控自由基聚合的高效、易获得的光催化剂。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.