Novel A-D-A structured triphenylamine derivatives for visible-LED photoinduced free radical polymerizations under air

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments Pub Date : 2025-09-17 DOI:10.1016/j.dyepig.2025.113248

Meng Yuan , Shenglian Zhu , Ran Chen , Minning Lan , Chen Yang , Changlin Zhou , XiaoJun Wang , Tao Xu , Lei Wang

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Abstract

The development of visible light initiation and anti-oxidative polymerization photoinitiators are in huge demand for the field of free radical polymerizations of acrylate. The A-D-A triphenylamine parent structure originated from our previous report, which depicted visible absorption and can largely consumed the ambient oxygen through efficient ISC process. On the other hand, CO₂ produced oxime esters by lighting induced N–O bond cleavage could further solved the oxygen inhibition problem. Herein, a series of A-D-A structured triphenylamine derivatives based from our parent structure (TPAs), containing oxime esters groups, was designed, synthesized, and applicated in the field of 450 nm LED photoinduced free radical polymerizations (FRP) under air. TPAs exhibit impressive photoinitiation ability verified by excellent polymerization rates and high final function conversion (FCs). Meanwhile, TPAs can act as both mono-component and two-component photoinitiating systems. The photophysical properties of TPAs are evaluated by UV, FL, and DFT theoretical calculations. Photochemical mechanism of TPAs are investigated by steady-state photolysis experiments, ESR, in situ ¹H NMR, cyclic voltammograms, LC-MS, and ATR-FTIR. Finally, the photoinitiating ability of TPAs is compared with commercialized photoinitiator OXE-01, indicating TPAs exhibited efficient anti-oxidative polymerization photoinitiation ability under visible light photoinitiation and demonstrating great commercial potential in the future.

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新型A-D-A结构三苯胺衍生物用于可见光led光诱导自由基在空气中聚合

丙烯酸酯自由基聚合领域对可见光引发剂和抗氧化聚合光引发剂的开发有着巨大的需求。A-D-A三苯胺母体结构来源于我们之前的报道，它描述了可见的吸收，并且可以通过有效的ISC过程大量消耗环境氧。另一方面，通过光照诱导N-O键裂解CO2生成肟酯可以进一步解决氧抑制问题。本文设计、合成了一系列a - d - a结构的三苯胺衍生物，这些衍生物是基于我们的母体结构（TPAs），含有肟酯基团，并应用于450 nm的LED光诱导自由基聚合（FRP）领域。优异的聚合速率和高的最终功能转换（FCs）证明了TPAs具有令人印象深刻的光引发能力。同时，tpa可以作为单组分和双组分光引发系统。通过UV、FL和DFT理论计算评价了tpa的光物理性质。通过稳态光解实验、ESR、原位1H NMR、循环伏安、LC-MS和ATR-FTIR研究了TPAs的光化学机理。最后，将TPAs的光引发能力与已商品化光引发剂OXE-01进行了比较，表明TPAs在可见光光引发下具有高效的抗氧化聚合光引发能力，未来具有很大的商业潜力。

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

Dyes and Pigments 工程技术-材料科学：纺织

CiteScore

8.20

自引率

13.30%

发文量

933

审稿时长

33 days

期刊介绍： Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied. Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media. The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.