Synthesis And Application Of Polymaleic Acid (Ester) Dyes

In this thesis, new polymaleic acid dyes and polymaleic ester dyes were designed and synthesized based on poly(maleic anhydride)(PMA). The two kinds of dyes were applied for dyeing cotton and polyester fabrics and the dyeing processes were researched in detail.Poly(maleic anhydride-co-(N-p-nitrophenyl)succinimide)(PMA-NO2) was synthesized by the reaction of PMA and4-nitroaniline. The nitro group in PMA-NO2was reduced by sodium dithionite, the resulting poly(maleic acid-co-(N-p-aminophenyl)succinimide)(PMA-NH2) was diazotized and coupled with1-(4’-sulfophenyl)-3-methyl-5-pyrazolone, N-benzoyl H acid and H acid-containing mono azo dye to synthesize yellow, red and blue polymaleic acid dyes PMA-DY1, PMA-DR1and PMA-DB1, respectively. Poly(maleic acid-co-(N-(1-(8-hydroxyl-3,6-disulfonic acid-naphthyl)succinimide))(PMA-H) was synthesized by reaction of PMA and H acid. PMA-H was coupled with aniline, sulfanilic acid,4-nitroaniline,4-methoxyaniline,2-aminothiazole,4-aminobenzonitrile and5-amino-1,3-dihydro-2H-benzimidazole-2-one diazo salts to synthesize red and purple polymaleic acid dyes PMA-DR2-6and PMA-DP1～2, respectively; while PMA-H was coupled with2-amino-5-nitrothiazole and3-amino-5-nitrobenzoisothiazole diazo salts to synthesize blue polymaleic acid dyes PMA-DB2-3, respectively. The structures of the polymaleic acid dyes were characterized by FT-IR and1H NMR. The grafting ratio of chromophore was determined by UV-vis standard curves, and the solubility of polymaleic acid dyes in water was determined.Poly(maleic anhydride-co-(N-(3-diethylamino-phenyl)succinimide)(PMA-N1) was synthesized by the reaction of PMA and3-amino-N,N-diethylaniline, then PMA-N1was coupled with4-nitroaniline,2-cyano-4-nitro aniline,2-amino-3-bromo-5-nitrobenzonitrile and3-amino-5-nitrobenzoisothiazole diazo salts to synthesize orange, red and purple polymaleic acid dyes PMA-DO1, PMA-DR7～8and PMA-DP3, which contain water insoluble chromophores, respectively. The grafting ratio of the chromophore was determined by UV-vis standard curves. Blue chromophore CB2was synthesized by the Ulmann reaction between1-bromo-4-(methylamino)anthraquinone and p-phenylenediamine, then it reacted with PMA to synthesize blue polymaleic acid dye PMA-DB4. After that, the polymaleic acid dyes were esterified by different kinds of alcohols to synthesize polymaleic ester dyes. Esterification of the polymaleic ester dyes was determined and the structures were characterized by FT-IR and1H NMR. The dyeing processes of the polymaleic acid dyes which cotain water soluble chromphores on cotton was researched, and polymaleic ester dyes which cotain water insoluble chromphores on polyester fabrics were also researched. The fixation ratio of polymaleic acid dyes on cotton could reach as high as98%when Zn(NO3)2and DICY were used as fixation agents. The wash fastness could reach grade4-5, and wet rub fastness could reach grade3-4. When the esterification degree of polymaleic ester dyes was up to30%, the dyeing properties were very good even at room temperature using a pigment dyeing process, due to the high affinity among polymaleic ester dyes, polyacrylate adhesives and polyester fabric. The dry and wet rub fastness could reach grade4-5and grade4, respectively. Also, the stiffness of dyed fabrics could be controlled by altering the monomer ratio in polyacrylate adhesives, and the dyeing fabrics feel good.