Synthesis And Application Of Polycarboxylic Acid Dyes And Polycarboxylic Ester Dyes

In this thesis, polycarboxylic acid dyes and polycarboxylic ester dyes were designed and synthesized. Polycarboxylic acid dyes were applied to dyeing of cotton fibre. As the dyes contain a certain number of reactive groups, a super-high dye fixation on cotton fibre was achieved through crosslinking dyeing and fixation. Polycarboxylic ester dyes were used for dyeing polyester fibre and showed good dye characteristics based on good compatibility of polycarboxylic ester dye and polyester fibre.Polymaleic anhydride (PMA) was synthesized with benzoyl peroxide (BPO) as free radical initiator and toluene as solvent. Its structure was characterized by FT-IR,1H NMR and gel permeation chromatography (GPC). In view of the problems existing in the synthesis process, such as high solvent consumption and low conversion, this thesis provided a technique for recycling the polymerization residue by analyzing the component and content of the solute in the residue. The results showed that it was possible to reuse the polymerization residue, with little change in the yield and the average molecular weight of the polymaleic anhydride produced in each cycle.Dye parent D1a was synthesized through diazotization and coupling reaction by using 3-nitroaniline as diazo component, and 1-phenyl-3-methyl-2-pyrazoline-5-one as coupling compound. Dye parent D1a was reduced to the corresponding amine compound D1b with toluene and water as component solvent and Na2S and NaHC03 as reducing agents. Greenization of the reduction process was realized thought a technique for recycling toluene solution and treating water solution.The structures of those dyes were characterized by IR, ’H NMR and API-ES mass spectroscopy. Polycarboxylic acid dye D1 was obtained thought amidation reaction by using PMA and D1b. The structure of D1 was characterized by UV and IR, and the results showed that the bridging group linking with PMA and chromophore was imide group. The synthesis methods of polycarboxylic acid dye D2, D3 and D4 were the same as that of polycarboxylic acid dye D1. Polycarboxylic ester dye D1-but was synthesized thought eaterification reaction by D1 and butanol, and esterificaiton degree reached 35% when polycarboxylic acid dye D1 with 35% grafting percentage was used as materials. The synthesis methods of polycarboxylic ester dye D2-but was the same as that of polycarboxylic ester dye D1-but.Physical and chemical properties of polycarboxylic acid dyes and polycarboxylic ester dyes were studied in this paper, and the results showed that polycarboxylic acid dyes with hydrophobic chromophore had soluble in water and normal organic solvent and hard soluble in saturated aliphatic hydrocarbon; polycarboxylic ester dyes with hydrophobic chromophore had soluble in nomal organic solvent and hard soluble in water and saturated aliphatic hydrocarbon; polycarboxylic acid dyes and polycarboxylic ester dyes with sulfonic acid group had soluble in strong-polar solvent such as water, acetic acid, DMF, and so on. Aqueous solution of polycarboxylic acid dyes possessed good stability when pH was 3-12 and temperature was below 60℃. The dyeing characteristics of polycarboxylic acid dyes on cotton were studied through padding operation. The fixation of the polycarboxylic acid dyes reached about 99%. The washfastness and dry rubfastness of polycarboxylic acid dyes reached 4-5 grade and 4-5 grade, respectively. Ball milled polycarboxylic ester dyes were studied and they gave satisfactory results. The dyeing characteristics of polycarboxylic ester dyes on polyester fibres were studied. The K/S value reached 10 and the washfastness and rubfastness of polycarboxylic ester dyes both reached 4 grade, and the fastnesses to sublimation were above 4 grade.