Study And Application Of Bifunctional Reactive Dyes With Sulfonamide-Containing Chloro-s-Triazine/Ethyl Sulfone Sulfate Groups

This thesis aims at improving the nucleophilic substitution reactivity of monochloro-s-triazine by introducing sulfonamide group into triazine ring.The electron density of triazine ring could be decreased by the electron withdrawing effect of sulfonamide group,which could lead to the improvement of nucleophilic substitution reactivity of monochloro-s-triazine.Firstly,2-N-benzene sulfonamide-4,6-dichloro-1,3,5-triazine was synthesized by the condensation of 2,4,6-trichloro-1,3,5-triazine with benzene sulfonamide,the condensation conditions were investigated in detail.The optimal condensation conditions were applied to the synthesis of 2-substituted-4,6-dichloro-1,3,5-triazine with the substitution of sulfonamide group,and the structure of the substituted dichloro-s-triazines was charterized by FT-IR,MS and 1H NMR.Their reactivity was investigated through methanolysis and the reaction with J-acid,y-acid and H-acid.The reaction rate constants obtained in methanolysis and reaction with J-acid,y-acid and H-acid proved that introduction of sulfonamide group enhanced the reactivity of the substituted dichloro-s-triazines.Secondly,the 2-substituted-4,6-dichloro-1,3,5-triazines were used to synthesize monoazo hetero-bifunctional reactive dyes by using the condensate of the substituted dichloro-s-triazines with J-acid or ?-acid as coupling component,and using 4-(ethylsulfurate sulfonyl)aniline as diazo component.Moreover,bisazo reactive dyes based on H-acid were synthesized by using the condensate of the substituted dichloro-s-triazines with 2,4-diaminobenzenesulfonic acid as diazo component,and using the acidic coupling product of H-acid and 4-(ethylsulfurate sulfonyl)aniline diazonium salt as coupling component.And the control dyes were obtained the same way simply by changing benzene sunlfonamide to ammonia hydroxide,aniline or sulfanilic acid.All the dyes were characterized by Uv-Vis,FT-IR and MS.Furthermore,DFT calculation was applied to simulate the molecular configuration and electron distribution of dyes.And the results of DFT calculation illustrated that the planarity of dye molecules decreased with the introduction of sulfonamide group.There was a dihedral between s-triazine ring and benzene ring of the benzene sulfonamide,which would increase the steric hindrance of fixation reaction between dyes and cellulose and then influence the increase in fixation.In addition,the Mulliken charge of s-triazine with the substitution of sulfonamide was alao more positive than that of the control group,which proved that the electron density was lower than that of the control group.The DFT calculation also demonstrated the nucleophilic substitution reactivity of monochloro-s-triazine could be improved by the incorporation of sulfonamide group.Thirdly,dyes involved in this thesis were used for the exhaust dyeing of cotton.The dyeing results showed that monoazo dyes based on J-acid and y-acid exhibited good substantivity to cotton cellulose,which has high exhaustion of 90%and above.And the exhaustion of biazo reactive dyes was about 85%.The fixation of dyes with the substitution of sulfonamide increased with the fixation temperature raising from 60? to 75?,and then decreased rapidly with the temperature raised to 90? due to the increase in hydrolysis of reactive dyes.But the fixation of the control group kept increasing with the fixation temperature from 60? to 90?.The dyeing results proved that monochloro-s-triazine substituted by sulfonamide had better temperature compatibility than that of the control group at lower dyeing temperature.In addition,the rub-fastness and wet-fastness of dyes with the substitution of sulfonamide group were about 1 grade higher than that of the control dyes,and the light-fastness was also 1 grade higher that of the rest dyes.