One-Component Stilbene-Based Iodonium Photoinitiators with Increased Photoacid Quantum Yield for Cationic Vat 3D Printing

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-10-17 DOI:10.1021/acs.macromol.4c01692

Filip Petko, Magdalena Jankowska, Mariusz Galek, Małgorzata Noworyta, Roman Popielarz, Joanna Ortyl

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引用次数: 0

Abstract

New advanced iodonium salts based on stilbene chromophores with significantly improved photoinitiating properties are presented. The extended conjugated double bond system provides major improvement in quantum yield of superacid generation (up to 10 times higher compared to benzylidene-based iodonium salts) while maintaining absorption properties in UV-A and visible light. The newly developed iodonium salts exhibit photoinitiating activity toward cationically polymerizable monomers such as cyclic epoxy monomers (e.g., 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane-carboxylate (CADE)), oxetanes (e.g., bis[1-ethyl(3-oxetanyl)]methyl ether (OXT-221)) and glycidyl ether monomers (e.g., diglycidyl ether of bisphenol A (DGEBA)) under the irradiation by light-emitting diodes (LEDs) emitting at 365, 405 and even 430 nm, with no additives. Commonly used diaryliodonium photoinitiators are inactive under those irradiation wavelengths. Moreover, some of the new iodonium salts are also able to photoinitiate free radical photopolymerization of the acrylate monomers, such as trimethylolpropane triacrylate (TMPTA). Such high photoinitiating activity allows these salts to be used as one-component photoinitiators in cationic vat 3D printing of nanocomposites at ambient temperature. The resolution of the cationic prints was limited mainly by the DLP 3D printer and monomers, with slight signs of overpolymerization.

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单组分链烯基碘鎓光引发剂提高了阳离子槽式 3D 打印的光酸量子产率

本文介绍了基于链烯发色团的新型高级碘盐，其光引发性能得到了显著改善。扩展共轭双键体系大大提高了超酸生成的量子产率（与亚苄基碘鎓盐相比可提高 10 倍），同时保持了紫外线-A 和可见光的吸收特性。新开发的碘盐对阳离子可聚合单体具有光引发活性，如环状环氧单体（如 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane-carboxylate (CADE)）、氧杂环丁烷（如、双[1-乙基（3-氧杂环丁酰）]甲基醚（OXT-221））和缩水甘油醚单体（如双酚 A 的二缩水甘油醚 (DGEBA)）。常用的二元碘鎓光引发剂在这些照射波长下不起作用。此外，一些新型碘盐还能光引发丙烯酸酯单体（如三羟甲基丙烷三丙烯酸酯（TMPTA））的自由基光聚合。如此高的光引发活性使得这些盐类可用作单组分光引发剂，在阳离子槽三维打印纳米复合材料时在环境温度下使用。阳离子打印的分辨率主要受到 DLP 3D 打印机和单体的限制，有轻微的过聚迹象。

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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.