【作者】 修景海；

【导师】 赵德丰；

【作者基本信息】 大连理工大学 ， 应用化学， 2003， 博士

【摘要】 金属络合染料是一类重要的染料分支，而偶氮金属络合染料，在整个金属络合染料中，当视为最重要的一类，主要用于蛋白质纤维（羊毛，蚕丝）和聚酰胺纤维的染色。传统的偶氮金属络合染料，含有铬、钴等重金属离子，在染料的合成及印染过程中，产生大量的有毒废水，严重危害周围水系的生态环境。自20世纪80年代以来，各国对纺织品中重金属离子Cr³⁺、Co²⁺含量进行了严格的限制；同时，由于铁盐的价格要远低于铬盐和钴盐，因此，研制新的环境友好的偶氮铁金属络合染料具有重要的意义。 本论文首先选择2-萘酚、1-苯基-3-甲基吡唑酮及1-（4-磺酸基苯基）-3-甲基吡唑酮作为偶合组份，分别与1-氨基-2-萘酚-4-磺酸（1，2，4酸）、2-氨基苯酚-4-磺酸以及邻氨基对硝基苯酚等重氮组份反应，合成7支用于偶氮金属络合染料合成的母体染料，利用电喷雾质谱、核磁共振和红外光谱等手段，对合成的母体媒介染料进行了结构鉴定。 以上述7支母体染料为中间体，合成8支1：1酸性偶氮铁、铬金属络合染料和14支1：2中性偶氮铁、铬金属络合染料，并运用大气压电喷雾质谱对所合成的14支1：2偶氮金属络合染料进行了结构表征。本论文对络合反应中各反应体系的条件进行了详细的研究。合成1：2偶氮铁金属络合染料反应体系的pH值在7.5～8.0之间，而1：2铬络合染料反应体系的pH值在9.0～10.0之间，反应温度均在75～80℃。1：2偶氮铁金属络合染料的收率达85％以上。 通过紫外-可见光谱分析，定性确认了母体染料的结构。并对金属络合染料进行了紫外-可见光谱的测试，其结果表明，偶氮金属络合染料的最大吸收波长λmax与母体染料相比较，均发生明显的位移，染料307和染料317，最大吸收波长λmax发生蓝移，其它的1：2偶氮金属络合染料的最大吸收波长λmax均发生红移，即向长波方向移动。偶氮铁金属络合染料与母体染料的摩尔消光系数emol值相差不大，偶氮铬络合染料的摩尔消光系数Cmol值则趋于降低。而且，由于金属离子的引入，1:2偶氮铁、铬金属络合染料的可见部分吸收谱带明显宽化，部分染料还有肩峰出现。 对14支l:2偶氮金属络合染料进行了大气压电喷雾质谱研究，采用软离子化技术，完成了对该系列化合物的准分子离子峰归属，并给出了这些化合物的准分子离子峰结构及分子量计算方法，对这类化合物的质谱特征做了定性的描述。质谱分析表明，对l:2偶氮金属络合染料的准分子离子峰构成一般为[M一xNa]x‘，或者[M一（x+y）Na+yH（K）]x一，x或（x+y）的最大值等于偶氮1:2金属络合染料所含的磺酸基个数加l，且x大于yo 所合成的1:1和l:2型铁金属络合染料均可用于羊毛和丝绸纤维的染色，其染色织物色泽饱满，色光纯正，在羊毛纤维上可获得黄棕、紫棕和黑棕等颜色。本论文探讨了铁金属络合染料在羊毛和丝绸纤维上的染色行为，研究了这些染料在羊毛纤维上的染色方法、染色工艺、上色曲线及其他染色性能，分别测定了它们在羊毛和丝绸纤维上的上色率、色度学数据及各项色牢度，并将铁和铬金属络合染料进行了比较。实验结果表明，偶氮铁金属络合染料在羊毛纤维的上色率均在85%以上，和相应的偶氮铬金属络合染料相当，且具有优良的日晒色牢度，良好的摩擦色牢度和耐洗色牢度。更多还原

【Abstract】 The metallized complexed azo dyes are important metallized complexe-d dyes used for protein (wool and siik) and polyamide fibers. Conventional metallized azo dyes, containing heavy metal ions such as chromium(III), cobalt(II) produce a large amount of industrial wastewater, which seriously polluting the ecological environment. Since 1980s, the contents of heavy metal ions Cr3+, Co2+ have strictly been limited in textile. So, it is very important to find environmentally friendly iron complex dyes as viable alternatives.In this paper, 2-NaphthoI, 3-methyl-1-phenyl-2-pyrazolin-5-one and 3-methyl-l-phenyl (4’-sulphol)-2-pyrazolin-5-one were selected as coupling components to react with respectively with the diazotization components, l-amino-2-naphthol-4-sulfonic acid, 2-aminophenol-4-sulfonic acid and 2-amino-4-nitrophenol to have synthesized to seven mordant dyes, for preparation of the metallized complexed azo dyes. Also, and the struct ures of the metallized mordant dyes were determined by IR, API-ES, NMR .The above-mentioned seven dyes were employed, as intermediates to complex respectively with chromium(III) and Iron(II) salts, to prepare eight 1:1 metallized complexed acidic azo dyes and fourteen 1:2 metallized neutral azo dyes prepared, among which the structures of the fourteen 1:2 metallized complexed azo dyes were determined by API-ES spectra. In synthesizing the 1:2 iron complex dyes, the pH value of reaction system was 7.5- 8.0 , whereas that in preparation of 1:2 chromium complex dyes was 9.0~10.0. Meanwhile the reaction temperature of 1:2 iron and chromium complex dyes was both 75-80℃C. The yield of 1:2 iron complex dyes based on presuror dyes was above 85.0%.By the visible spectra analysis, the structure of the precursor dyes were determined and the metallized complexed dyes characterized, whichshowing that the maximum absorption wavelength of metallized complexes shifts obviously in the corresponding position compared with that of the precursor dyes. The dyes 307 and 317 exhibited hypsochromic shift in X max, compared with that of the corresponding metal-free parent compounds, while other 1:2 metallized complexed dyes all had bathochromic shift in the position of major absorption band along with broadening of the absorption curves. The molar extinction coefficient e ) of 1:2 Fe complexes did not change obviously, compared with those of the parent dyes.By atmospheric pressure electrospray ionization and soft ionization technology, the fourteen 1:2 metallized complexed azo dyes were studied, pseudo-molecular ion peaks of the compounds reasonably assigned, the calculation methods of pseudo-molecular ion peaks and molecule weights suggested, and their spectra characters described qualitatively, which indicating that 1:2 metallized complexed azo dyes either formed molecular ions with different charges by subsequent loss of protons, i.e. [M-xNa]x~, or formed adducts with hydrogen ions, i.e. [M-(x+y)Na+yH(K)]x", and the maximum value of x or (x+y) was the sum of number of sulphonic acid groups and one, in which x was larger than y.The application of 1:1 and 1:2 Fe complexed dyes to wool and silk fabrics was satisfactory, through measuring, the light fastness, washing fastness and rubbing fastness of the dyed wool and silk proved good, which showed that fastness properties were similar to those of the corresponding chromium complexes. The experiment displayed that the exhaustion of all these dyes is over 85% in the 3%(o.w.f%), The colors generated on wool by using 1:1 andl:2 Fe complex dyes were from light brown, dark purple to brown black.更多还原