CN101381525B - Method for preparing vat yellow 2 anthraquinone thiazole dyes - Google Patents
Method for preparing vat yellow 2 anthraquinone thiazole dyes Download PDFInfo
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- CN101381525B CN101381525B CN2007100455454A CN200710045545A CN101381525B CN 101381525 B CN101381525 B CN 101381525B CN 2007100455454 A CN2007100455454 A CN 2007100455454A CN 200710045545 A CN200710045545 A CN 200710045545A CN 101381525 B CN101381525 B CN 101381525B
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- anthraquinone
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- vat yellow
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- thiazole dyes
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Abstract
The invention provides a method for preparing vat yellow 2 anthraquinone thiazole dye. in the presence of cuprous chloride as catalyst, after reacting in a 1.3-dimethyl-2-imidazolinone (DMI) solvent for 6 to 8 hours at the temperature between 130 and 180 DEG C, 2, 6-diaminoanthraquinone, benzenyl trichloride and sulfur with the molar ratio of 1:2-3.5:3.5 are diluted by use of a DMI solution, cooled to room temperature, filtered, treated by use of concentrated sulfuric acid with the concentration of 98 percent for 2 to 3 hours at the temperature between 60 and 75 DEG C, washed, filtered, oxidized by use of a sodium hypochlorite aqueous solution with the concentration of 10 percent for 2 to 3 hours at the temperature between 60 and 75 DEG C, filtered , washed and dried, and then the vat yellow 2 anthraquinone thiazole dye is obtained. The yield of the dye is 70 to 75 percent, and the strength of the dye is 244 to 252 percent.
Description
One, technical field
The present invention relates to the preparation method of a kind of vat yellow 2 anthraquinone thiazole dyes (vat yellow2CI67300), relate to 2 or rather, and the 8-diphenylanthrancene [2,1-d; 6,5-d '] double thiazole-6, the preparation method of 12-diketone.
Two, background technology
Vat yellow 2 anthraquinone thiazole dyes is a kind of green glow yellow, color clear, avidity is strong and the yellow dyes of good level-dyeing property.
The preparation method of vat yellow 2 anthraquinone thiazole dyes has several synthetic routes.Prior art JP09-003351,07.01,1997, with 2,6-diamino-anthraquinone and Benzoyl chloride and Sodium sulfhydrate prepared in reaction, reactor product thermosol are cooled off precipitated crystal then in aqueous sulfuric acid, wash neutrality, dry filter block obtains distinct xanchromatic vat yellow 2 anthraquinone thiazole dyes.This method is made solvent with chlorobenzene, needs logical chlorine 12 hours in the reaction process, although say so industrial very useful method, logical chlorine substitution reaction neither the ideal method, needs to improve.
Domestic a lot of producer adopts the technology of the IG dyestuffs industries stock company that is positioned at Frankfurt, Germany, and this method is solvent with the refined naphthalene, and cupric chloride is a catalyzer, and by 2,6-diamino-anthraquinone and benzenyl trichloride (trichlorotoluene zotrichloride), sulphur carry out condensation.Carry out using sulfuric acid dissolution, dilution again behind the heat filtering with fusion naphthalene dilution, then with hypochlorite oxidation, at last after filtration, drying and standardization make product.This method is solvent with the refined naphthalene, and it is a kind of solvent of volatile, easy distillation, reclaims difficulty, the general rate of recovery has only 70%, and, in the long-time reactor product quality of high temperature instability, the dyestuff yield that makes according to this method is 62%, and dye strength is 215～220%.At this on the one hand, select novel solvent to replace the refined naphthalene solvent to become the needs of each manufacturer.
Three, summary of the invention
Present inventors have proposed the improvement technical scheme through long-time research to the technology of German IG dyestuffs industries stock company, and prescription and solvent have been done improvement.At first 2, the mol ratio of 6-diamino-anthraquinone, benzenyl trichloride (trichlorotoluene zotrichloride) and sulphur is 1: 2～3.5: 3.5.Solvent adopts 1, and 3-dimethyl-2-imidazolone (DMI), this solvent are a kind of colourless transparent liquid, the strong non-proton inert solvent of polar, and boiling point has hypotoxicity and excellent in chemical character and thermostability up to 225.5 ℃.Dye strength with the vat yellow 2 anthraquinone thiazole dyes of its preparation is 224～252%, yield 70～75%, and solvent recovering rate is 85%.And the refined naphthalene rate of recovery of corresponding background technology is 70%.
Chemical equation of the present invention is as follows:
2.6-diamino-anthraquinone and benzenyl trichloride and sulphur are in the presence of cuprous chloride catalyst, 1, in 3-dimethyl-2-imidazolone solvent in 130～180 ℃ the reaction 6～8 hours after, reaction solution is with 1,3-dimethyl-2-imidazolone solvent cut, be cooled to room temperature, filter, handled 2～3 hours in 60～75 ℃ with the 98 weight % vitriol oils, washing, filtration, with the 10 weight % potassium hypochlorite aqueous solution in 60～75 ℃ of oxidation 2-3 hours, filtration, washing, dry vat yellow 2 anthraquinone thiazole dyes.
Solvent 1,3-dimethyl-2-imidazolone and 2, the weight ratio of 6-diamino-anthraquinone is 1～4: 1.
The present invention compared with the prior art, temperature of reaction is low, the reaction times is short.The intensity height of gained dyestuff, the yield height.The solvent recovering rate height, quality product is more stable.
Four, embodiment
Especially exemplified by example it is described in order to implement the present invention better, but embodiment not a limitation of the present invention.
Embodiment 1
10.4g2 6-diamino-anthraquinone (content 96 weight %), 20g benzenyl trichloride, 5g sulphur, 0.2g cuprous chloride and 15g1,3-dimethyl-2-imidazolone (DMI) mix mutually, slowly be warming up to 140 ℃, be incubated 2 hours, be warming up to 160 ℃ again, be incubated 3 hours, be warming up to 180 ℃ at last, be incubated 2 hours, add 30ml DMI dilution, reducing to room temperature filters, use 60mlDMI, the filter wash cake blots.Wash DMI in the most filter cake with clear water again, filter cake is put into 150g98 weight % sulfuric acid stir, be warming up to 70 ℃, be incubated 2 hours, material is diluted in the 350g clear water, filter, filter cake is washed to neutrality.Get filter cake and add water 80g making beating, add 35g chlorine bleach liquor (10 weight %), be warming up to 75 ℃ of oxidations 2 hours, filter, be washed to neutrality.The dry vat yellow 2 anthraquinone thiazole dyes dry product 14g that gets, weight yield is 70% of a theoretical amount, dye strength 244%, coloured light is identical with standard.
Embodiment 2
10.4g2 6-diamino-anthraquinone (content 96 weight %), 26g benzenyl trichloride, 5g sulphur, 0.2g cuprous chloride mix mutually with 20gDMI, slowly are warming up to 160 ℃, are incubated 6 hours, subsequent operations is identical with embodiment 1.Get vat yellow 2 anthraquinone thiazole dyes dry product 14.6g, weight yield is 73% of a theoretical amount, dye strength 252%, and coloured light is identical with standard.
Embodiment 3
10.4g2 6-diamino-anthraquinone (content 96 weight %), 30g benzenyl trichloride, 5g sulphur, 0.2g cuprous chloride mix mutually with 30gDMI, slowly are warming up to 140 ℃, are incubated 2 hours, are warming up to 160 ℃ again, are incubated 4 hours, subsequent operations is identical with embodiment 1.Get vat yellow 2 anthraquinone thiazole dyes dry product 15g, weight yield is 75% of a theoretical amount, dye strength 250%, and coloured light is identical with standard.
Claims (2)
1. the preparation method of a vat yellow 2 anthraquinone thiazole dyes, it is characterized in that 2,6-diamino-anthraquinone and benzenyl trichloride and sulphur are in the presence of cuprous chloride catalyst, 1, in 3-dimethyl-2-imidazolone solvent, in 130～180 ℃ of reactions 6～8 hours, 2, the mol ratio of 6-diamino-anthraquinone, benzenyl trichloride and sulphur is 1: 2～3.5: 3.5; Reaction solution is with 1,3-dimethyl-2-imidazolone solvent cut, be cooled to room temperature, filtration, handled 2～3 hours in 60～75 ℃ with the 98 weight % vitriol oils, washing, filtration, with 10 weight % aqueous sodium hypochlorite solutions in 60～75 ℃ of oxidation 2-3 hours, filtration, washing, dry vat yellow 2 anthraquinone thiazole dyes.
2. the preparation method of vat yellow 2 anthraquinone thiazole dyes according to claim 1 is characterized in that described solvent 1,3-dimethyl-2-imidazolone and 2, and the weight ratio of 6-diamino-anthraquinone is 1～4: 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100455454A CN101381525B (en) | 2007-09-03 | 2007-09-03 | Method for preparing vat yellow 2 anthraquinone thiazole dyes |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100455454A CN101381525B (en) | 2007-09-03 | 2007-09-03 | Method for preparing vat yellow 2 anthraquinone thiazole dyes |
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| CN101381525A CN101381525A (en) | 2009-03-11 |
| CN101381525B true CN101381525B (en) | 2011-02-02 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103589191A (en) * | 2013-11-08 | 2014-02-19 | 上海华元实业总公司 | Novel method for post-processing vat yellow GCN |
| CN105693530A (en) * | 2014-11-27 | 2016-06-22 | 江苏华尔化工有限公司 | Synthesis method of 1,4-diamino-2,3-dichloro-dichloroanthraquinone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2097867A (en) * | 1935-11-25 | 1937-11-02 | Du Pont | Preparation of anthraquinone dithiazoles |
| US2289292A (en) * | 1940-05-14 | 1942-07-07 | American Cyanamid Co | Process of preparing anthraquinone dithiazoles |
| US2453410A (en) * | 1944-03-13 | 1948-11-09 | American Cyanamid Co | Acid treatment of anthraquinonethiazole vat dyestuffs |
-
2007
- 2007-09-03 CN CN2007100455454A patent/CN101381525B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2097867A (en) * | 1935-11-25 | 1937-11-02 | Du Pont | Preparation of anthraquinone dithiazoles |
| US2289292A (en) * | 1940-05-14 | 1942-07-07 | American Cyanamid Co | Process of preparing anthraquinone dithiazoles |
| US2453410A (en) * | 1944-03-13 | 1948-11-09 | American Cyanamid Co | Acid treatment of anthraquinonethiazole vat dyestuffs |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平9-3351A 1997.01.07 |
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Granted publication date: 20110202 Termination date: 20200903 |