有机鎓盐掺杂铝酸锶基蓝色光夜光纤维的制备及机理研究

The blue-light luminous fiber doped with organic onium salt is made by using a photoinitiator material with conjugated structure, strontium aluminate strontium oxide materials and polymer substrate, which can emit blue light in the dark after being excited by light. At present, only the rare earth strontium aluminate luminous fiber with yellow-green light has been appeared, and has achieved industrial production, but the disadvantage is lack of the red and blue light. As a kind of organic photoinitiator, triarylsulfonium salts capable of being decomposed by light, then generate chromophores, which become a hot spot in the research of new materials. From previous studies it is found that triaryl sulfonium salt can make the blue-shift of light color of the rare earth strontium aluminate luminescent material. However, blue-light luminous fiber is prepared doping with triaryl sulfonium salt first, its light –emitting principle is not very clear and the blue-light emitting performance has yet to be further improved. This topic mainly prepares an blue-light rare earth aluminate strontium fiber through improving dispersion state of the triarylsulfonium salt and luminous material inside the fiber to improve the energy transfer efficiency from the light conversion agent to luminous materials .The basic research is studied by the ratio of the raw materials, the molecular structure, melting temperature, excitation conditions and other factors, which can affect the light-color performance of the fiber. The project is aimed at revealing the energy transfer mechanism within the fiber, and further explore its light-emitting mechanism. The research achievements will establish theoretic and technical foundation for the development of blue-light fiber.

有机鎓盐掺杂的蓝色光夜光纤维是利用含有共轭结构的光引发材料、稀土铝酸锶发光材料和聚合物基材制备的一种受光激发后在黑暗处可以发出蓝色光的功能纤维。目前，仅有黄绿色光的稀土铝酸锶夜光纤维，并已经实现了产业化生产，缺少作为三原色的红色光和蓝色光。三芳基硫鎓盐作为一种有机光引发材料，能够受光分解产生生色团，成为新兴材料研究的热点。申请人通过前期研究发现，该光引发材料能够使稀土铝酸锶发光材料的光色产生蓝移，但作为掺杂剂制备的蓝光纤维，其发光原理尚未清楚且发光性能也有待进一步提高。课题拟以三芳基硫鎓盐与改性后的稀土铝酸锶发光材料通过高温熔融作用结合制备蓝光纤维，通过改善三芳基硫鎓盐光引发剂和发光材料在纤维内部的分散性能以提高光引发剂向发光材料转变的能量传递效率，并对影响纤维光色性能的原料配比、分子结构、熔融温度、激发条件等因素进行研究，旨在揭示纤维内部的能量传递机制从而阐明蓝光发光原理，为研制三原色之一的蓝色光夜光纤维奠定理论和技术基础。

项目采用微波煅烧法制备了稀土铝酸锶发光材料，并对其进行硅烷偶联剂改性，将改性后的发光材料与三芳基硫鎓六氟锑酸盐、聚丙烯基材共混后经熔融纺丝制备出蓝色光夜光纤维，考察了三芳基硫鎓六氟锑酸盐对稀土夜光纤维光谱蓝移的影响因素和蓝移原理，并对影响纤维光色性能的原料配比、分子结构、熔融温度、激发条件等因素进行研究。结果表明，在稀土夜光纤维中掺杂三芳基硫鎓六氟锑酸盐，能够使夜光纤维的发射光谱和发光色谱蓝移。当三芳基硫鎓六氟锑酸盐含量达到0.5% 时，发射光谱开始向短波方向移动，光色产生蓝移。掺杂三芳基硫鎓六氟锑酸盐稀土夜光纤维的发射光谱为宽带双光谱，发射峰位于440nm和520nm附近，分别归属于三芳基硫鎓六氟锑酸盐光解生成π电子的瞬态发射峰和稀土发光材料Eu2+离子4f65d1→4f7的跃迁发光。掺杂三芳基硫鎓六氟锑酸盐稀土夜光纤维的发光机制较复杂，纤维内部存在三芳基硫鎓六氟锑酸盐和发光材料之间的能量传递，并伴随着一系列的光化学反应，发光颜色为二者发射光叠加后的混合光色。