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由红光和近红外光驱动的稳健微乳液光原子转移自由基聚合反应

Robust Miniemulsion PhotoATRP Driven by Red and Near-Infrared Light.

作者信息

Hu Xiaolei, Yin Rongguan, Jeong Jaepil, Matyjaszewski Krzysztof

机构信息

Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.

出版信息

J Am Chem Soc. 2024 May 15;146(19):13417-13426. doi: 10.1021/jacs.4c02553. Epub 2024 May 1.


DOI:10.1021/jacs.4c02553
PMID:38691625
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11099965/
Abstract

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 ≤ ≤ 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.

摘要

光诱导聚合技术因其温和的条件、时空可控性和简单的装置而备受关注。除了均相介质外,人们还努力在乳液中实现光聚合,使其成为一种实用且更环保的工艺。然而,以往在非均相介质中的光诱导可逆失活自由基聚合(RDRP)依赖于穿透深度有限的短波长光,导致聚合速度慢且控制效果相对较差。在本研究中,我们展示了首例在空气中由红色或近红外(NIR)光驱动的高效光诱导微乳液原子转移自由基聚合(ATRP)。这得益于水溶性光催化剂亚甲基蓝(MB)的使用。在水溶性电子供体存在的情况下,红色/近红外光照射可使MB有效激发,并随后将ATRP失活剂光还原,从而引发和介导聚合过程。近红外光驱动的微乳液光ATRP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光穿透对不同尺寸反应器和大规模反应(250 mL)中聚合动力学的影响,突出了长波长光,特别是近红外光在分散介质中大规模聚合方面的优势,因为其具有卓越的穿透性。这项工作为强大的乳液光聚合技术开辟了新途径,提供了一种更绿色、更实用的方法,具有更好的控制和更高的效率。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/a0e269a5ac98/ja4c02553_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/c6bc74c1d906/ja4c02553_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/5c94b3a5cfdc/ja4c02553_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/81081db3401e/ja4c02553_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/cfc442e20f3a/ja4c02553_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/a0e269a5ac98/ja4c02553_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/c6bc74c1d906/ja4c02553_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/5c94b3a5cfdc/ja4c02553_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/81081db3401e/ja4c02553_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/cfc442e20f3a/ja4c02553_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7065/11099965/a0e269a5ac98/ja4c02553_0004.jpg

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引用本文的文献

[1]
Red Light-Driven, Oxygen-Tolerant RAFT Polymerization Enabled by Methylene Blue.

J Am Chem Soc. 2025-9-3

[2]
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ACS Biomater Sci Eng. 2025-8-11

[3]
Near-Infrared to Visible Photon Upconversion with Gold Quantum Rods and Aqueous Photo-Driven Polymerization.

J Am Chem Soc. 2025-8-6

[4]
Open-Air Growth of Polymer Brushes by Surface-Initiated PhotoATRP under Red-Light Irradiation.

ACS Appl Mater Interfaces. 2025-7-2

[5]
Brush-modified fluorescent organic nanoparticles by ATRP with rigidity-regulated emission.

Chem Sci. 2025-4-30

[6]
ATRP with ppb Concentrations of Photocatalysts.

J Am Chem Soc. 2024-10-23

[7]
Highly efficient dual photoredox/copper catalyzed atom transfer radical polymerization achieved through mechanism-driven photocatalyst design.

Nat Commun. 2024-6-17

本文引用的文献

[1]
Photocatalytic Activation of Aryl(trifluoromethyl) Diazos to Carbenes for High-Resolution Protein Labeling with Red Light.

J Am Chem Soc. 2024-1-17

[2]
Composition-Orientation Induced Mechanical Synergy in Nanoparticle Brushes with Grafted Gradient Copolymers.

Macromolecules. 2023-11-29

[3]
Red-Light-Driven Atom Transfer Radical Polymerization for High-Throughput Polymer Synthesis in Open Air.

J Am Chem Soc. 2023-11-8

[4]
Biomass RNA for the Controlled Synthesis of Degradable Networks by Radical Polymerization.

ACS Nano. 2023-11-14

[5]
Near-Infrared Light-Induced Reversible Deactivation Radical Polymerization: Expanding Frontiers in Photopolymerization.

Adv Sci (Weinh). 2023-11

[6]
Inverse Miniemulsion Enables the Continuous-Flow Synthesis of Controlled Ultra-High Molecular Weight Polymers.

ACS Macro Lett. 2023-9-19

[7]
RNA-Polymer Hybrids via Direct and Site-Selective Acylation with the ATRP Initiator and Photoinduced Polymerization.

J Am Chem Soc. 2023-7-5

[8]
Multiblock copolymer synthesis RAFT emulsion polymerization.

Chem Soc Rev. 2023-5-22

[9]
Photocontrolled RAFT polymerization: past, present, and future.

Chem Soc Rev. 2023-5-9

[10]
Visible Light-ATRP Driven by Tris(2-Pyridylmethyl)Amine (TPMA) Impurities in the Open Air.

Macromol Rapid Commun. 2023-8

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