Synthesis And Application Of Polyvinylamine Macromolecule Self-crosslinking Dyes With High Light Stability

In this thesis, two kinds of polyvinylamine macromolecule self-crosslinking dyes were designed and synthesized based on poly(NV-vinylformamide-co-vinylamine) and poly(vinylamine-co-crylic acid). They were applied for dyeing cotton fibers and high fixation as well as high light stability were achieved due to their self-crosslinking abilities.Firstly, low molecular weight polymers of poly(N-vinylformamide) and poly(N-vinylformamide-co-crylic acid) were synthesized by precipitation polymerization and the influences of synthesis conditions on the yield and molecular weight of polymers were investigated. Then the polymers prepared in the optimal conditions were hydrolyzed in hydrochloric acid and sodium hydroxide solutions, respectively. The hydrolyzed products of poly(N-vinylformamide-co-vinylamine) with the mole fraction of amino group of 79.5% and the number average molecular weight of 1240.5 and poly(vinylamine-co-crylic acid) with the mole fraction of amino group of 78.7% and the number average molecular weight of 1088.2 were obtained.Three azo chromophores of DR1, DB1 and DY1 with excellent water-solubility and other three azo chromophores of DR2, DB2 and DY2 containing cyano group as well as one azo chromophore of DB3 containing thiazole structure were designed and prepared using cyanuric chloride as the linking group. All these chromophores were characterized by UV-Vis, FT-IR and MS. Moreover, a new kind of seven H-acid monoazo-anthraquinone reactive dyes of 7a?g and one azo-anthraquinone chromophore of DB4 were designed and synthesized by using 1,4-bis((4-aminophenyl)amino)anthrancene-9,10-dione or 1-((4-aminophenyl) amino) -4-hydroxy-anthrancene-9,10-dione as diazo component and H-acid derivatives as coupling components. All these dyes were characterized and the results showed that the maximum absorption wavelengths of the dyes were all about 590 nm, which indicated that they were a kind of blue dyes. 1H NMR and 13C NMR results and density functional theory (DFT) calculations proved the formation of the new larger conjugated system from which the blue colour was generated.Eight macromolecular self-crosslinking dyes P(NVF-VAm)-DR1?2/DB1?4/DY1?2 and eight macromolecular dyes P(VAm-AA)-DR1?2/DB1?4/DY1?2 were synthesized by grafting reaction of poly(N-vinylformamide-co-vinylamine) and poly(vinylamine-co-crylic acid) with eight different chromophores, respectively. By controlling the reaction process, the high grafting ratios of about 30% were realized, and the structures of the synthesized macromolecular dyes were characterized by IR and thin layer chromatography. The macromolecular self-crosslinking dyes were used for dyeing cotton fibers using a dip-pad-steam process without crosslinking agent. The fixation of the red, blue or yellow dye on cotton fibers could reach up to 93.5%,96.0% and 99.0%, respectively. Dry and web rub fastness were 4 grade and 3 grade above, respectively, and wash fastness was above 4 grade. The light fastness of the dyed fibers were tested and the results showed that the light fastness of poly(N-vinylformamide-co-vinylamine) dyes containing cyano group or anthraquinone chromophore on cotton were improved by 0.5?2 grade and the light fastness of poly(vinylamine-co-crylic acid) dyes containing carboxy groups were improved by 0.5?1.5 grade, of which the light fastness of red, blue and yellow poly(vinylamine-co-crylic acid) dyes on cotton was 3?4 grade,4?5 grade and 6?7 grade, respectively. All these results will provide a new way for the synthesis of reactive dyes with high fixation on cotton and excellent light stability.