Research On Synthesis And Properties Of Fe、Al Metal-Complexed Dyes

The metallized complex azo dyes have been used widely in protein （wool andsilk） and polyamide fibers because of their great light fastness, washing fastness andrubbing fastness. The azo metallized complex dyes are one of the most importantmetallized complex dyes. The conventional azo complex dyes usually contain heavymetal ions such as chromium （Ⅲ） and cobalt （Ⅱ）. These metal ions produce a largeamount of industrial wastewater, which is hazardous to human and is a seriouspollutant to ecological environment. Since 1980s, the contents of heavy metal ionshave strictly been limited in textile. Therefore, it is very important and interesting tosynthesize new metallized complex azo dyes which are environmental friendly, suchas iron aluminum complex azo dyes, since these salt derivates have an advantage ofnon-toxicity or low-toxicity and economic feasibility.Aromatic amine was usually synthesized in water or organic solvent. Theprocedure was complex, redundant, and caused environmental pollution. Therefore,it is urgent to simplify the synthetic process and decrease the amount of pollution.Ionic liquids, as green solvents, are used to synthesize organic intermediates anddyes in place of classical organic or water solvents. This contributes significantly toboth the environment and green chemistry.Firstly, we focused on the reductive reaction of nitro group substituted aromaticcompounds to aromatic amines using ionic liquid. It was demonstrated that theprocedure of the synthesis of amine using ionic liquid as media was moderate withhigh yields. Furthermore, unlike the volatile organic compounds, because the ionicliquids are salts that are liquids at room temperature, they have negligible vaporpressure and can be reused repeatedly. The experimental results showed that theionic liquid could be used repeatedly three times without affecting the yield of the product. Hence, it is a perfect green solvent.Secondly, 1, 3, 5-pyrazolone, chloro substituted pyrazolone,p-methylpyrazolone, m-sulfonic acid pyrozolone, and m-sulfamide were selected ascoupling components to react respectively with the diazotization components, suchas 1-amino-2-napHthol- 4-sulfonic and orthanilic acid to afford 8 mordant dyes. Onthe other hand, o-aminobenzoic acid, 2-amino-5-nitrophenyl hydroxide, 2-amino-4-chloro-5-nitrophenyl hydroxide, N, N,-disubstituted aniline, and isophthalamide waschose as diazotization components to react with bisnaphthol respectively tosynthesize 4 mordant dyes. The 12 mordant dyes mentioned above, were furtheremployed as intermediates to complex with aluminum （Ⅲ） and iron （Ⅱ） saltsrespectively. Sixteen 1 : 2 Fe、Al complexed pyrazolone’s azo dyes and eight 1 : 1Fe、Al complexed bisnaphthol azo dyes were made. Among the dyes complex, ten ofthem were made for the first time. All the structures of the dyes were determined byIR, ES, NMR, Power diffraction.At the same time the complex reaction conditions were optimized, and theexperimental results showed that the best choice for 1:1 reaction system was at pH 3,while for the 1:2 reaction system was at pH 7.0～8.0. Yields obtained were morethan 80%Through testing of absorbance of the metal complex dyes, results indicated thatλ_max of the metal complex dyes was transferred, comparing with the mother’s bodydyes. The AI complex dyes of the mother’s dyes of D, E, F, G were red-translocation,while the corresponding Fe complex dyes were blue-translocation, and all the othermetal complex dyes were red-translocation. In additional, the intensity of absorbancediffered when comparisons with the mother’s body dyes were made. All the metalcomplex dyes of the mother’s body dye of A-C2 lost its luster, and the metalcomplex dyes of the mother’s body dye of C3 had its luster intensity increased. TheAl complex dyes of the other mothers’ body dyes increased its luster as well, whilethe Fe complex dyes lost its luster.Thirdly, the quantitative structure activity relationship （QSAR） of thepyrazolone’s dyes was discussed. Twenty-two most stable conformations were optimized with the theory of quantum chemistry. The excited state was calculatedusing the time-dependent density functional theory （TD-DFT） method at theLanL2MB base set lever. The excited state energies and transition wave lengths ofdifferent conformations of seven ligands were obtained. These results offer newtheoretical evidence up to the further study on the relation of the structure andchromophoric properties of dyes.Lastly, all of the metal complex dyes were applied to dye cotton and wool. Thecolor and luster was full and the light colors were pure. The wool-dyeingmethodology and technology were studied including dye pH values, temperature andtime. The perfect condition of the dyeing procedure was found. The test resultsproved the azo Fe、Al complex dyes’ had a dyeing rate above 85%. This iscomparable with Cr complex dyes. Fe and Al complex dyes also had excellent lightfastness, excellent rubbing fastness and washing fastness. When compared with Crcomplex dyes with Fe, Al complex dyes, the latter were environment friendly.