Synthesis And Application Of Metal-complexed Crosslinking Dyes

In this thesis, metal-complexed crosslinking dyes containing polyamine groups were designed and synthesized. They were prepared by introducing the metal ions onto the molecules of crosslinking dyes which contained the reactive amino and imine groups. As the dyes contain a certain number of reactive groups, a super-high dye fixation on fibre is expected to be achieved through crosslinking dyeing and fixation, and the greenization of the dyeing process may be realized. At the same time, the light fastness of the crosslinking dyes is expected to be improved due to the existence of metal ions within the dye molecules.Dye parents la and 2a were synthesized through diazotization and coupling reaction by using 3-amino-4-hydroxy benzenesulfonic acid as diazo component, and 3-methyl-1-phenyl-2-pyrazolin-5-one and 4-(4-hydroxy-3-methyl-1H-pyrazol-1-yl)benzenesulfonic acid as coupling componds, respectively. Dye parents 3a and 4a were synthesized through diazotization and coupling reaction by using 2-amino-4-nitrophenol as diazo component, and 4-(4-hydroxy-3-methyl-1H-pyrazol-1-yl)benzenesulfonic acid and 2-hydroxynaphthalene-3,6-disulfonic acid as coupling componds, respectively. The structures of these dye parents were characterized by IR, ¹H NMR and API-ES mass spectroscopy.Four chlorosulfonyl-containing azo compounds (1b-4b) were synthesized by the reactions of the corresponding sodium sulfonate of acid dyes and thionyl chloride in the presence of a catalytic quantity of DMF. Their structures were confirmed by IR, ¹H NMR and API-ES mass spectroscopy. The effects of reaction time and the amounts of the solvent and DMF on the reaction were discussed. Four polyamine crosslinking dyes 1c-4c were synthesized from the prepared chlorosulfonyl-containing compounds and tetraethylenepentamine. The structures of dyes 1c-4c were characterized by IR spectroscopy.Four metal-free crosslinking dyes 1c-4c were complexed with chromium salt and iron salt, respectively, to get four new Cr-complexed crosslinking dyes ld-4d and four new Fe-complexed crosslinking dyes 1e-4e. The structures of these metal-complexed crosslinking dyes were confirmed by IR and atomic absorption spectroscopy (AAS). The visible spectra of the crosslinking dyes before and after the complex reaction were studied by UV-Vis spectroscopy.Copper phthalocyanine (CuPc) crosslinking dye was synthesized through the reaction of chlorosulfonyl-containing copper phthalocyanine dye with tetraethylenepentamine. Its structure was confirmed by IR spectroscopy. The effects of reaction temperature and the molar ratio of CuPc to HSO₃Cl to SOCl₂ on the amount of chlorosulfonyl group in CuPc were discussed. The effects of reaction time, temperature, the molar ratio of the amount of chlorosulfonyl group in CuPc to tetraethylenepentamine and the amount of the solvent on amination reaction were studied.Some polyamine crosslinking metal-complexed dyes were used to dye silk and wool through salt-free exhaustion dyeing. The effects of pH value, temperature, the liquor ratio and the concerntration of dyes on the dyeing performance were discussed. The exhaustion of some Fe-complexed crosslinking dyes on silk reached 99% and on wool reached 97%, respectively. With use of DAST as fixation agent, the effects of pH value and the concerntration of DAST on fixation were discussed. The crosslinking reaction of Fe-complexed crosslinking dyes on silk and wool all reached 98%. The fixation ratio of Fe-complexed crosslinking dyes on silk and wool reached 97% and 95%, respectively. The light fastness of Fe-complexed crosslinking dyes on silk and wool was 2-3 grade higher than that of the corresponding metal-free crosslinking dyes. The wash fastness of Fe-complexed crosslinking dyes was a little higher than that of the corresponding metal-free crosslinking dyes. The rub fastness of Fe-complexed crosslinking dyes was comparable with that of the corresponding metal-free crosslinking dyes. The dyeing performance and fastness properties of Fe-complexed crosslinking dyes were comparable with that of Cr-complexed crosslinking dyes. The exhaustion of the dyed silk and wool using copper phthalocyanine crosslinking dye was high. The lightfastness, wash fastness and rub fastness of the copper phthalocyanine crosslinking dye on silk and wool were satisfactory.