Synthesis And Application Of Polyamine And Polycarboxylic Acid Dyes

In this thesis, the polyamine and polycarboxylic acid dyes were designed andsynthesized. They were prepared by grafting the chromophores onto the molecules containingreactive amino and carboxylic groups. As the dyes contain a certain number of reactivegroups, a super-high dye fixation on fibre is expected to be achieved through crosslinkingdyeing and fixation which realizes the green dyeing.The red crosslinking polyamine dye was synthesized by using tetraethylenepentamineand reactive red X-3B. The effects of temperature and the pH value on the yield of the dyewere discussed, and the hydrolysis of reactive dye was well controlled.A series of novel red polyamine crosslinking dyes based on benzoyl H-acid sulfonamidewere prepared via the reaction of it with diazo salts of aniline, p-toluidine, o-methoxyaniline,p-aminophenol, p-nitraniline, m-aminobenzene sulfonic acid and1-aminonaphthalene-5-sulfonic acid, respectively. Effects of reaction time, temperature,solvents and pH value on benzoylation, chlorosulfonation and amination had been discussedin this paper and the synthesis methods had been determined.Two ehlorosulfonyl-eontaining pyrazolone azo compounds were synthesized by thereactions of the corresponding sodium sulfonate of acid dye and thionyl chloride in thepresence of a catalytic quantity of DMF. Their structures were confirmed by IR, ~1H NMR andMS spectroscopy, and the results revealed that the obtained sulfonyl chlorides existed instable hydrazone form. Two polyamine crosslinking dyes (2-3b and 2-4b) were synthesizedfrom the prepared chlorosulfonyl-containing compounds and tetraethylenepentamine(Schotten-Baumann reaction).Blue crosslinking dye was synthesized by the reaction of tetraethylenepentamine with1,4-dihydroxy anthraquinone. Effects of reaction time, temperature and solvent werediscussed and the synthesis methods were established.With use of DAST as fixation agent, the dyeing performance of polyamine crosslinkingdyes on silk and cotton were studied through salt-free dipping or padding operation. Thefixation ratio of partial polyamine crosslinking dyes reached 99%, the washfastness andrubfastness of polyamine crosslinking dyes reached 4grade and 4-5 grade, respectively.The free radical polymerization of acryloyl chloride in cyclohexane withazobisisobutyronitrile as initiator yielded solid polyacryloyl chloride under a dry nitrogenatmosphere. The effects of concentration of monomer and the mole ratio of initiator to monomer on polymerization of acryloyl chloride were investigated. Their structures wereconfirmed by IR spectroscopy.Two red polycarboxylie acid dyes were prepared by reacting polyacryloyl chloride withH-acid in water-acetone solution followed by coupling with sulfanilic acid and p-toluidine inwater solution. Finally acryloyl chloride was hydrolyzed into carboxyl groups. Synthesis ofyellow polycarboxylic acid dye was similar to that of the red one. The blue one wassynthesized with polyacryloyl chloride and disperse blue E-2RL as reactants instead.The dyeing characteristics of polycarboxylic acid dye on cotton were studied throughpadding operation. The fixation of the polycarboxylic acid dyes reached about 85%. Thewashfastness, dry rubfastness of polycarboxylic acid dyes reached 4-5grade and 4-5grade,respectively.