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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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Executive Summary


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.

Full-text Catalog


Summary     5-10
ABSTRACT     10-20
Chapter Preface     20-55
1.1 Overview disperse dyes     20-21
1.2 azo disperse dyes structure property relationship     the 21-23 1.2.1 azo dye structure and color
relationship     21-22
1.2.2 even the relationship between the structure of nitrogen dye sublimation-resistant performance     22
1.2.3 the azo dyes structural and sun-resistant properties of the relationship between     22-23
1.3 azo disperse dyes Research progress     23-29
1.3.1 heterocyclic azo disperse dyes     24-26
1.3.2 Functional azo disperse dyes     26-29
1.4 indole ketones application     29-36
1.4.1 indole-2 - ketone compounds synthesized     29-33
1.4.2 Application having biological activity indole ketones     33-36
1.5 containing indole -2 - ketone structure the synthesis method of the compound and disperse     36-44
1.5 .1 containing indole -2 - ketone structure Synthesis   the   36-41
1.5.2 azo disperse dyes synthetic     41-44
1.6 This thesis content and significance     44-46
1.6.1 research topics are found;   44-45
1.6.2 research significance of     45-46
Reference     46-55
Chapter II indole-2 - one Synthesis and Factors Influencing     55-79
2.1 Introduction     55
2.2 Experimental     55-61
2.2.1 Reagents and instruments     55-57
2.2.2 Experimental methods     57-61
2.3 Results and discussion     61-76
2.3.1 recrystallization solvent and the melting point of the product and the yield     61-62
2.3.2 product 4a-4f element analysis     62
2.3.3 sodium sulfate dosage intermediates 2a-2f yield   the   62-63
2.3.4 dehydration of concentrated sulfuric acid cyclization temperature of intermediates 3a-3f yield     the nbsp the 63-65 2.3.5
middle intermediates 2'a-2'f yield;   65
2.3.6 three synthetic indole -2 - ketone compound method     the 65-68 2.3.7 NMR spectra
Analysis   the   68-70
2.3.8 crystal structure, characterization     70-76
2.4 Summary     76-77
Reference     77-79
Chapter Containing Indole -2 - ketone structure synthesis and influencing factors of disperse dyes     79 - 102
3.1 Introduction     79-81
the 3.2 Experimental     the 81-87 3.2.1 Reagents and Instruments
    81-82
3.2 .2 Experimental Method     82-87
3.3 Results and discussion   the   87-98
3.3.1 various solvents and the melting point of the intermediates and the final product was recrystallized     analysis of the elements of each product in 87-89
3.3.2     89
3.3.3 NMR spectral analysis of the product     89-94
3.3.4 catalyst and synthesis method on the yield of product 5a-5c     94-95
3.3.5 of different-reduction product 6a-6c yield     95
3.3. 6 different diazotization product yield     95-96
3.3.7 nitrobenzaldehyde synthesis mechanism     96-98
3.4 Summary     98-99
Reference     99-102
fourth chapter containing indole-2 - ketone structure of disperse dyes, optical properties, and post-processing     102-120
4.1 Introduction     nbsp optical properties of
4.1.1 disperse dyes, 102-106;   the 102-103
4.1.2 disperse dyes, the post-processing     103-106
4.2 Experimental     106-109
4.2.1 Reagents, materials and instruments     106-107
4.2.2 Experimental Method     107-109
4.3 results and discussion     109-117
4.3.1 indole-2-- ketone azo disperse dyes UV - visible absorption spectroscopic properties     109-112
4.3. 2 dispersant on the particle size and particle size distribution of the dye     112-113
4.3.3 dispersant dosage size and size distribution of the dye     113
4.3 .4 milling time, particle size and particle size distribution of the dye     113-114
4.3.5 milling dye system stability studies     114-115
4.3.6 The   dye particle size of the dye levelness impact   115
4.3.7 dye staining K / S values ??and levelness are found;   115-117
4.4 Summary     References 117-118
    118-120
Chapter containing indole-2 - ketones structure of disperse dyes dyeing performance     120-147
5.1 Introduction     121
5.2 Experimental     121-125
5.2.1 Reagents, materials and instruments     121-122
5.2.2 Experimental Method     122-125
5.3 results and discussion     125-144
5.3.1 hot melt dyeing fixation rate and K / S values ??    125-126
5.3. 2 hot melt dyeing fastness     126
5.3.3 high-temperature and high-pressure dyeing dye uptake and K / S values ??    5.3.4 high-temperature and high-pressure dyeing dyeing. 126-127
the rate curve     the deep curve nbsp 127-131
the 5.3.5 high temperature high pressure dyeing dyeing delivery;   131-132
5.3.6 high temperature high pressure dyeing fastness     132 -133
5.3.7 dye polyester fabric dyeing kinetics     the 5.3.8 high temperature high pressure dyeing thermodynamics nbsp 133-138
;  
5.3.9 dye, 138-142 acetate fiber dyeing performance     142-144
5.4 Summary     144-146
Reference     146-147
Chapter VI Conclusion     147-149
BRIEF 1 Compound 4a-4f ~ 1HNMR Spectrum     149-155
BRIEF 2 Compound A1-A4, B1-B4 and C1-C4 ~ 1HNMR Spectrum     to post 155-167
Dr. during     167-168
thank the     168

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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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