芳香族二硫化物光吸收及光引发性能研究  

Photoabsorption and photoinitiation properties of aromatic disulfides

作　　者：鞠小兵 张玉含 孙芳 JU XiaoBing;ZHANG YuHan;SUN Fang(College of Chemistry,Beijing 100029;Anqing Research Institute,Anqing 246000,Beijing University of Chemical Technology,China)

机构地区：[1]北京化工大学化学学院,北京100029 [2]北京化工大学安庆研究院,安庆246000

出　　处：《北京化工大学学报（自然科学版）》2022年第6期14-22,共9页Journal of Beijing University of Chemical Technology(Natural Science Edition)

基　　金：国家自然科学基金(52073018)。

摘　　要：以二苯二硫醚(PDS)、对甲苯二硫醚(MPDS)、2,2′-二氟二苯二硫醚(FPDS)、5,5′-二硫代双(2-硝基苯甲酸)(DTNB)、2,2′-二硫二吡啶(PDDS)和双(2-噻吩基)二硫醚(TPDS)这6种芳香族二硫化物为对象,研究了它们的光吸收和光引发性能,分析了供电子基团、吸电子基团、富电子五元芳杂环和缺电子六元芳杂环对硫自由基光引发活性的影响。结果表明:这6种芳香族二硫化物的最大吸收波长均小于300 nm,供电基团甲基及芳香杂环的引入使芳香族二硫化合物的最大吸收波长红移,吸电子基团氟原子和硝基等使最大吸收波长蓝移;在385 nm的发光二极管(LED)照射下PDS、MPDS、DTNB和PDDS均能发生二硫键的断裂而产生芳基硫自由基,而TPDS不能生成稳定的芳基硫自由基;在385 nm的LED照射下PDS、MPDS、FPDS、DTNB和PDDS均能引发三丙二醇二丙烯酸酯(TPGDA)和三羟甲基丙烷三丙烯酸酯(TMPTA)聚合,在405 nm的LED照射下也可以引发TPGDA聚合;TPDS不能引发TPGDA和TMPTA聚合。The photoabsorption and photoinitiation properties of six aromatic disulfides, diphenyl disulfide(PDS), p-toluene disulfide(MPDS), 2,2′-difluorodiphenyl disulfide(FPDS), 5,5′-dithiobis(2-nitrobenzoic acid)(DTNB), 2,2′-dithiodipyridine(PDDS) and bis(2-thienyl) disulfide(TPDS), have been studied. The effects of electron-donating groups, electron-withdrawing groups, electron-rich five-membered aromatic heterocycles and electron-deficient six-membered aromatic heterocycles on the photoinitiation activity of the sulfur radicals were analyzed. The results show that the maximum absorption wavelengths of the six aromatic disulfides are all below 300 nm. The introduction of the electron-donating methyl and aromatic heterocycle groups leads to a red shift in the maximum absorption wavelength of the aromatic disulfides, whilst the introduction of the electron-withdrawing fluorine and nitro substituents causes a blue shift in the maximum absorption wavelength. Irradiation of PDS, MPDS, DTNB and PDDS with a 385 nm light-emitting diode(LED) leads to fission of the disulfide bond and generates aryl sulfide radicals, while TPDS does not form stable aryl sulfide radicals. Under 385 nm LED irradiation, PDS, MPDS, FPDS, DTNB and PDDS can initiate the polymerization of both tripropylene glycol diacrylate(TPGDA) and trimethylolpropane triacrylate(TMPTA). Under 405 nm LED irradiation, they can also initiate TPGDA polymerization. However, TPDS cannot initiate the polymerization of TPGDA or TMPTA.

关 键 词：芳香族二硫化合物 LED光聚合 光引发剂 光吸收性能 光引发活性 

分 类 号：TQ572.4[化学工程—精细化工] TQ630.1TQ323