【作者】 秦传香；

【导师】 陈国强； 王筱梅；

【作者基本信息】 苏州大学 ， 纺织化学与染整工程， 2009， 博士

【摘要】 在众多的有机非线性光学材料中,分子结构一端是供电子基团,而另一端是受电子基团的氨基取代苯乙烯吡啶盐（简称苯乙烯吡啶盐）在科学与技术应用领域有很多成功的应用。氨基取代苯乙烯吡啶盐类衍生物也是潜在的光致二阶非线性光学材料,可以用于制造兼有线性荧光和非线性荧光性能的多功能材料。但是,就作者的知识面而言,还没有见到将氨基取代苯乙烯吡啶盐应用于制备荧光纤维（织物）的报道。在本论文中,作者合成了11种氨基取代苯乙烯吡啶盐,并尝试通过不同途径制备含有这些苯乙烯吡啶盐的荧光纤维材料。主要研究内容和结论包括以下四个部分:1)首先合成了11种苯乙烯吡啶盐,并确认它们的分子结构。其次,测试了这些化合物的光学性质,包括溶液态的线性/非线性光学性质、固体粉末的荧光发射光谱。随着苯乙烯吡啶盐染料分子结构中供电子基团上羟基的增加,染料的紫外吸收光谱和单光子荧光发射光谱有蓝移趋势;而随着受电基团上亚甲基数目的增加,染料的紫外吸收光谱和单光子荧光发射光谱的波长位置变化很小。阴离子不仅影响染料的溶解性,而且也影响光学性质。随着溶剂极性的增强,苯乙烯吡啶盐染料紫外吸收光谱发生蓝移、单光子荧光发射光谱发生红移、荧光强度下降、荧光量子产率下降的趋势。6种苯乙烯吡啶盐染料的DMF溶液具有明显的双光子吸收现象;通过Z-扫描测试计算出苯乙烯吡啶盐染料DHEASPT-C₈的非线性吸收系数β与三阶非线性极化率系数x^（3）分别为3.09×10^-11m/W和4.78×10^-12 esu。2)在比较温和的聚合反应条件下,合成出苯乙烯吡啶盐染料基团接在聚合物侧链上的聚酰亚胺齐聚物（PI-C₁、PI-C₈）和聚硅氧烷齐聚物（SI-C₄）,它们在300℃以前有很好的热稳定性。它们有明显的紫外吸收峰和单光子荧光发射峰,相对于原来的苯乙烯吡啶盐染料,聚酰亚胺齐聚物的吸收峰峰位和荧光发射峰峰位发生了明显的蓝移,而聚硅氧烷齐聚物没有明显的不同。3)采用传统的阳离子染料染色工艺,将部分水溶性苯乙烯吡啶盐染料用于腈纶织物染色和真丝绸染色,所染织物的耐晒牢度为2级,但是染色织物的反射率曲线中发射区域的反射率大于100%,表明它们具有相似于商业荧光染料—荧光黄X-10GFF提供荧光效果的能力。苯乙烯吡啶盐染料在腈纶织物上的吸附属于Langmuir型吸附;随着荧光染料分子中吡啶盐端所接的烷基链长的增加,上染速度变缓,上染率增加。4)把苯乙烯吡啶盐染料掺杂到成纤聚合物（聚酰胺酸、聚乙烯醇、聚乳酸、聚氯乙烯、聚氨酯）溶液中,通过静电纺丝工艺可以制备出荧光纤维膜,纤维直径处于纳米级范围。为了提高静电纺丝膜荧光的稳定性,合成出两种无机荧光粉(Eu₂WO₆和NaCaPO₄:Eu²⁺),并制备出掺杂有Eu₂WO₆的荧光纤维膜。更多还原

【Abstract】 Among various organic NLO materials,aminostyrylpyridinium salts （stilbene-type dyes,hemicyamine dyes）,possessing donor group on one end and acceptor group on the other end,had found some successful application in science and technology.That their derivatives also are promising materials for the photo-induced second-order optical effects,which allows expecting that they may be used as multi-functional materials,possessing both linear and non-linear fluorescence. However,to the best of the authors’ knowledge,there is no report about the application of aminostyrylpyridinium salt to fluorescent fiber（fabric）.In this article, we present eleven aminostyrylpyridinium salts,with an electron donor（disubstituted amino） and an aromatic acceptor moiety joined by a flexible bond.The goal is to prepare fluorescent fiber using these 11 aminostyrylpyridinium salts.Main Conclusions contained four parts as follows.1).Firstly,eleven aminostyrylpyridinium salts have been synthesized and their structures have been confirmed.Then their optical properties in solution and aggregation were investigated.Results showed that OH-in donor groups had bigger effect on linear optical properties of dyes than substituted amine in acceptor groups, and the anion had influence on both solvability and optical properties.With the increase of the solvent polarity parameter,the absorption spectra were blue-shifted,the fluorescence spectra were red-shifted and there had an obvious decrease in fluorescence intensity and fluorescence quantum yield.Six dyes in DMF possess good TPA behaviors and the non-linear optical experimental results of DHEASPT-C₈ by the Z-scan technique at 532 nm showed that the NLO absorption coefficientβwas 3.09×10^-11 m/W and the third-order NLO coefficient x^（3） was 4.78×10^-12 esu.2) In the facile reacting condition,two kind oligomers,polyimide and polysiloxane, attached with aminostyrylpyridinium salt group were synthesized successfully.And they all had obvious fluorescent properties.As polyimide oligomer is concerned,there were some blue shifts of characteristic peaks that corresponded to hemicyanine dyes in the UV spectra and fluorescence spectra.But there is no obvious change in polysiloxane oligomer.3) Acrylic fabrics and silk fabrics were dyed with several water-soluble aminostyrylpyridinium salts following conventional dyeing procedure of cationic dyes. The light colorfastness of dyed fabrics was evaluated according to the AATCC TM 16-2003 standard method,and the results showed that the colorfastness of all three samples was only grade 2.The reflectance of the dyed fabrics exceeded 100%in the emission range and four aminostyrylpyridinium salts had the similar ability to produce fluorescence as the Yellow X-10GFF.The adsorption of aminostyrylpyridinium salts onto acrylic fibers was found to follow a Langmuir mechanism,and the dye uptake and sorption rate increased with increasing alkyl chain length of the dye molecule.4) A series fluorescent mats had been made through electrospinning process by adding aminostyrylpyridinium salts to fibre-forming polymers.The diameters of fibers selected from the electrospun mats were in nanometer scopes.To improve the stability of electrospun mats,inorganic phosphors,Eu₂WO₆ and NaCaPO₄:Eu²⁺,were synthesized and the optical properties of both inorganic phosphors and electrospun mats containing Eu₂WO₆ had also been discussed.更多还原