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Synthesis and Application Study of Disperse Dyes with Indole-2-one Structure

Author: SunJie
Tutor: CaiZaiSheng
School: Donghua University
Course: Textile Chemistry and Dyeing and Finishing Engineering
Keywords: Indolin-2-one Disperse Dyes Synthesis Dyeing Application
CLC: TQ613.24
Type: PhD thesis
Year: 2010
Downloads: 117
Quote: 0
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Disperse dyes, which named cellulose acetate dyes, appeared in market in period of 1920s for the development of cellulose acetate fiber. With the development of PA, PAN, especially PET fiber, disperse dyes developed rapidly. Now disperse dyes are mainly dyes for PET dyeing and printing. In azo disperse dyes, for the purpose of promoting shade brilliance and enriching color spectrum, besides some substitute groups were introduced into dye structure, some heterocyclic compounds were introduced into dye structure as diazo component or coupling component to synthesize some heterocyclic azo disperse dyes. Heterocyclic azo disperse dyes contains some special properties, which common dyes don’t have, such as fluorescence property, optical property, thermochromic property and photosensitivity. Indolin-2-one belongs to Five-membered heterocyclic and is an important medical and pesticide intermediate. Indolin-2-one derivatives were widely used as pharmacophore in medicine. There is rarely research on introduction indolin-2-one into disperse dyes. In this article, indolin-2-one compounds were synthesized successfully and a series of disperse dyes containing indolin-2-one structure prepared, the post-treatment process and the dyeing properties of these dyes were studied. The article contains four parts, and each section is described below.In the first part, indolin-2-one compounds (4a-4f) were synthesized with anilines as raw material, via three methods which were Friedel-Crafts alkylation, Wolff-Kishner-Huang Ming-long tow-step reduction and Wolff-Kishner-Huang Ming-long one-pot reduction. Effect factors of these three synthesis methods were studied and the optimal process to synthesize indolin-2-one compounds was found. The results showed that, besides arose salting-out effect and accelerate product precipitation, sodium sulfate played an important role on the balance of electric charge in reaction system when intermediate N-isonitrosacetanilide (2a-2f) was preparing. The yield of intermediates 2a-2f was highest and reached 80% and over when amount of sodium sulfate was 340g/L. Isatin compounds (3a-3f) was prepared from compounds N-isonitrosacetanilide (2a-2f). When dehydration and cyclization temperature of concentrated sulfuric acid is 85-90℃,the yield of Isatin compounds (3a-3f) was highest and reached 90% and over. When cyclization temperature was too low, raw material didn’t react completely, so the yield was low. When reaction temperature was too high, the amount of by-products increased. During the preparation of intermediates 2-chloro-N-phenyl-acetamide(2’ a-2’ f) with anilines and Chloroacetyl Chloride, acetic acid was the optimum react medium, the yield of products (2’a-2’f) was 94% and over. By comparing three synthesis methods of indolin-2-one compounds (4a-4f), it showed that the yield was high and reached 80% and over when synthesis was performed via isatin and Huang Ming-long reduction, especially with triethylene glycol as react solvent and one-pot reduction without separation of intermediates hydrazone compounds.The second part is about the synthesis of disperse dyes with indolin-2-one structure.12 monoazo disperse dyes (Al-A4、B1-B4、C1-C4), which contain indolin-2-one structure, were synthesized with indolin-2-one(4a), 5-bromoindolin-2-one (4b),5-fluoroindolin-2-one (4c) as raw materials. The synthesis course contained Knoevenagel condensation with 3-nitrobenzaldehyde, nitro reduction, diazotization-coupling reaction. The synthesis process of intermediates and final products was mainly researched. The structure of products (Al-A4、B1-B4、C1-C4) was affirmed by H’NMR. The results showed that 3-nitrobenzaldehyde could be synthesized by an indirect nitrification with ammonia as protective agent for aldehyde group and the yield reached 99%. With ionic liquid DBUBr (1,8-Diazabicyclo[5,4,0]undec-7-ene bromide) as a catalyst, the yield of 3-(3-nitrobenzylidene)indolin-2-one compounds (5a-5c) are highest and reached 95% and over. Without catalyst, the yield of 3-(3-nitrobenzylidene)indolin-2-one compounds (5a-5c) by microwave synthesis method reached 90%. When compounds (5a-5c) were reduced by stannous chloride and with concentrate hydrochloric acid/acetic acid as react solvent, the yields of compounds 3-(3-aminobenzylidene)indolin-2-one (6a-6c) were maximal and reached 75% and over.When synthesis the monoazo disperse dyes A1-A4, the yield of three diaz diazotization-coupling methods (sodium nitrite/ concentrate hydrochloric acid, nitrosyl sulfuric acid/ mixed acid, sodium nitrite/ concentrate sulfuric acid) were almost equal and approached 80%. On the other hand, during the synthesis of monoazo disperse dyes B1-B4 and C1-C4, the yield of nitrosyl sulfuric acid/ mixed acid was higher than that of other two methods and above 80%.That third part is about the optical property and post-treatment of disperse dyes. The synthesized disperse dyes were milled and the effect of dispersant kinds and amounts, milling time on dyes particle sizes and particle size distributions was studied. The research result showed that monoazo disperse dyes(A1-A4, B1-B4, C1-C4) with indolin-2-one structure have optical absorption property at wave range 420~460nm. The maximal absorption wave length of dyes A1-A4 increased gradually when N-substituted groups of aniline changed. From dye B1 to dye B4, dye C1 to dye C4, the maximal absorption wave length of dyes decreased gradually while N-substituted groups of aniline changed. Dispersant plays an important role on milling effect of dyes. When the mass ratio of Dispersant NNO and sodium lingosulfonate was 1:2, the average particle size was near lum, the particle size was more level and particle size distribution index was minimal. When the mass ratio of Dispersant and dyes was 1:1, the average particle size and distribution index was minimal. The average particle size and distribution index decreased with the milling time extension, after milled 48 hours, the particle size was under 0.5 um. The optimal milling process of dyes (Al-A4、B1-B4、C1-C4) was established. Aqueous solution of 1% dye was milled at 20℃for 36 hours, the ratio of dispersant and dye was 1:1, dispersant was composed by NNO and sodium lignosulfonate with ratio 1:2, the frequency of milling machine was 1000Hz. After milled, the dyes have good high temperature dispersivity and centrifugal stability. The level property of milled dyes in high temperature and pressure dyeing process was fine and the mean square error was lesser than 1. The dyed fabrics reached eligible textile request.The fourth part is about the dyeing properties of disperse dyes. The pad-dry-cure dyeing property, high temperature and pressure dyeing property of these 12 kinds of dyes on PET fabrics were investigated, as well as their dyeing property on acetate cellulose fiber. Dyeing kinetics and dyeing thermodynamics of 12 kinds of dyes on PET fabrics were research as well. The results showed that the fixation rate and color fastnesses of dyes (A1-A4, B1-B4, C1-C4) on PET fabrics with pad-dry-cure dyeing were good. The pad-dry-cure dyeing fixation of dyes A1-A4 were over 85%, dyes B1-B4 between 75% and 80%, dyes C1-C4 near 85%. The exhaustion percent of dyes (A1-A4、B1-B4、C1-C4) on PET fabrics with high temperature and pressure dyeing were over 70%, and the color fastnesses were good. The build up property of dyes (A1-A4、B1-B4、C1-C4) are good. The fastest stage of dyeing rate of dyes A1-A4 was 40-80 min, dyes B1-B4 60-100 min, dyes C1-C4 40-100 min.The chemical structure of dye molecules exerts an influence on the dye sorption properties. After dyeing dynamic research, it was found that dyes A1-A4 approached dyeing equilibrium after dyeing 40 min, dyes B1-B4 and C1-C4 60 min. The dyeing rate constant of dyes A1, B1 and C1 were bigger than those of dyes A2-A4, B2-B3 and C2-C4 respectively.With the dyeing thermodynamics research, it found that the concentration of dyes on fiber and the concentration of dyes in dyebath manifested good linear relation. The adsorption of dyes on PET fiber was Nernst distribution adsorption, namely non-orientation adsorption. With the increase of dyeing temperature, more dyes adsorbed on fiber and the distribution coefficient increased.The exhaustion percents of dyes A1-A4, B1-B4 and C1-C4 on acetate cellulose fiber were over 90%, the migration and level property of dyes on acetate cellulose fiber was good. After dyeing, the color fastnesses of fabric were good, the dry and wet rubbing fastness, soap fastness were 4-5 grade and over, the sublimation fastness of dyes were 5 grade except dyes A1, A2 and C1 were 4-5 grade, the light fastness of dyes reached 7-8 grade.

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CLC: > Industrial Technology > Chemical Industry > Dyes and intermediates industry > Synthetic dyes of various structures > Anthraquinone dye > Disperse dyes
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