CN101906258A - Method for producing acid dye - Google Patents
Method for producing acid dye Download PDFInfo
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- CN101906258A CN101906258A CN201010216157XA CN201010216157A CN101906258A CN 101906258 A CN101906258 A CN 101906258A CN 201010216157X A CN201010216157X A CN 201010216157XA CN 201010216157 A CN201010216157 A CN 201010216157A CN 101906258 A CN101906258 A CN 101906258A
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Abstract
The invention relates to a method for producing an acid dye of a formula (III), which comprises the following steps of: (1) performing first coupling reaction on nitroaniline diazonium salt and H acid to obtain compound solution of a formula (I); (2) performing second coupling reaction on DASA diazonium salt and the compound solution of the formula (I) to obtain compound solution of a formula (II); (3) performing third coupling reaction on m-phenylenediamine and compound solution of the formula (II) to obtain compound primary pulp of the formula (III); and (4) performing spray drying on the compound primary pulp of the formula (III) to obtain compound primary powder of the formula (III). By optimizing the spray drying method, the method is a pollution-free production process, which does not generate waste slag and process wastewater, simplifies the process flow, reduces the investment of equipment, improves the production efficiency and saves the production cost.
Description
(1) technical field
The present invention relates to a kind of production method of matching stain.
(2) background technology
The common problem that matching stain exists in process of production is to produce waste water, ecotope is caused detrimentally affect, people attempt to eliminate or weaken negative impact to environment by the mode of shutting down, stop, merge and change or the mode of carrying out technological transformation, this effort never is interrupted, the social needs harmonious development, living needs is colorful, and people's clothing be unable to do without colourful, and the direction of dyestuff development must stride forward towards process for cleanly preparing.
The traditional production method of erie black NT (C.I.Acid Black 210) is the magma that obtains crude product by multistep diazonium, coupled reaction, the latter through saltout, filter, dry, a plurality of post-processing steps such as pulverizing obtain former powder, this method separates out former dyestuff owing to add a large amount of industrial refined salt, filter again, produce a large amount of filtrates and washing lotion and formed waste water, salt content height in the waste water, COD content is also high, reach emission standard, must take a series of control techniquess, the production cost of enterprise obviously increases, and large batch of production is hard to carry on especially.
(3) summary of the invention
Technical problem to be solved by this invention provides that a kind of production process is succinct, with low cost, the matching stain production method of clean and environment-friendly.
A kind of production method of the matching stain suc as formula (III) comprises the steps:
(1) p-Nitroaniline diazonium salt and H acid are carried out first time coupled reaction and are obtained formula (I) compound solution;
(2) DASA diazonium salt and formula (I) compound solution carries out second time coupled reaction and obtains formula (II) compound solution;
(3) mphenylenediamine and formula (II) compound solution carries out for the third time that coupled reaction obtains formula (III) compound magma;
(4) formula (III) compound magma spraying drying is promptly got the former powder of formula (III) compound.
Formula of the present invention (III) matching stain is erie black C.I.210 dyestuff, and p-Nitroaniline English abbreviates PNA as, and DASA is 4, the English of 4 '-diaminobenzene sulfonanilide is called for short, H acid refers to 1-amino-8-naphthol-3, the 6-disulfonic acid, and mphenylenediamine English abbreviates MPD as.
Preferably, the solid content of described formula (III) compound magma is 10-30%.
Again preferably, the solid content of described formula (III) compound magma is 15-22%.
Preferably, the molar ratio of described raw material is p-Nitroaniline: H acid: the DASA diazonium salt: mphenylenediamine=1: 0.8-1.2: 0.8-1.2: 0.7-1.0.
Preferably, the feed way of described three step coupled reactions is respectively: the H acid solution adds in the p-Nitroaniline diazonium salt solution, formula (I) compound solution joins in the DASA diazonium salt solution, mphenylenediamine joins in formula (II) compound solution with solid-state form.
Preferably, the pH value of step (1) coupled reaction is 0.5-1.5, and the pH value of step (2) coupled reaction is 3.0-7.0, and the pH value of step (3) coupled reaction is 6.0-10.0.
Again preferably, the pH value of step (1) coupled reaction is 0.8-1.0, temperature of reaction 5-8 ℃, and reaction times 5～10h; The pH value of step (2) coupled reaction is 4.5-5.5, temperature of reaction 5-8 ℃, and reaction times 2～5h; The pH value of step (3) coupled reaction is 6.0-7.0, temperature of reaction 5-8 ℃, and reaction times 1～3h.
Preferably, the color base purity of described former powder is greater than 80%, and former powder power part is 150-180%.
Synthetic route and conventional production methods that the present invention adopts have than big-difference, mainly show: adjusted production technology parameter and ingredient proportion, improved feeding mode, optimized and respectively go on foot reaction pH value; Reduce unnecessary supplementary material consumption, reduced salt content; Reaction solution magma without saltout, filter, dry, pulverize supervisor, directly enter spray-drying tower and remove moisture and obtain former powder.The impurity of remaining interference coloured light is few in the reaction solution magma, and color base purity height just can satisfy specification of quality and industry standard without filtering separating impurity, because reaction solution magma solid content is higher, adopts direct spray-drying process promptly to obtain former powder.
Beneficial effect of the present invention is
1) the present invention does not produce waste residue and processing wastewater owing to optimized the process for cleanly preparing that adopts spray-drying process, belongs to environmentally friendly machine;
2) the present invention has abandoned salting-out procedures, filtration operation, drying process and the pulverizing process in the existing production technique, has simplified technical process, has reduced the input of equipment, has improved production efficiency;
3) the present invention has optimized ingredient proportion, has improved the selectivity and the color base purity of reaction, has reduced consumption of raw and auxiliary materials, has saved industrial salt, has saved production cost.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
1) adding 60g water in the 250ml flask is opened and is stirred, and adds 25.0g86%H acid, making beating 5min, and adding 9.0g30% liquid caustic soda is molten entirely to H acid, transfers pH=6.5 standby.
2) in another 250ml flask, add 30g water, open and stir, add 9.0g 99% p-Nitroaniline (PNA), add the 30g trash ice behind the making beating 0.5h, be cooled to 0-5 ℃, add 0-5 ℃ of 22.5g31% hydrochloric acid control then, treat the complete molten back of PNA disposable adding 4.9g 97% Sodium Nitrite (being made into 30% aqueous solution), keep and add the 0.5g thionamic acid behind the reaction 30min and make PNA diazonium liquid.
3) above-mentioned PNA diazonium liquid is changed over to the 500ml flask, add dissolved H acid solution then, below 10 ℃, pH value 0.8-1.0 reacts 8h with the frozen water controlled temperature.HPLC detects (I) purity 94.7%
4) DASA of adding 60g water and 15.69g folding hundred in another 500ml flask, making beating 0.5h adds 60g trash ice and 34.5g 30% hydrochloric acid, when temperature is reduced to 2-3 ℃, disposable adding 9.0g97% Sodium Nitrite (being made into 30% aqueous solution) keeps stirring reaction 0.5h below 5 ℃.Add the 0.6g thionamic acid again, obtain DASA diazonium liquid.
5) add a conjugates by the gross in the 500ml flask that DASA diazonium liquid is housed, reinforced finishing then adds about 9.2g 30% liquid caustic soda and transfers pH=4.5-5.5.Holding temperature 5-8 ℃ of reaction 3h obtains two conjugates.HPLC detects the purity 88.3% of (II)
6) add about 5g30% liquid caustic soda in above-mentioned secondary coupled reaction thing and transfer pH=6-7, add 6.8g99%MPD subsequently, reinforced finishing gets three conjugates at 5-8 ℃ of reaction 2h.HPLC detects the purity 86.0% of (III).
7) three conjugates magma sabots oven dry gets former powder 92g.Product is converted to mark product 94.9g (by power part 180%).Chromatic light deviation Δ C is 0.066.
Embodiment 2:
In embodiment 1, the coupled reaction part of front is identical, and gained three conjugates are heated to 80-90 ℃, adds refined salt 30g, cools to room temperature behind the insulation 0.5h and filters, and filter cake is dried then, pulverized with 200g3% salt water wash, gets former powder 73.6g.Be converted to mark product 92g.Chromatic light deviation Δ C is 0.451, and coloured light is slightly gorgeous.
Embodiment 3:
In embodiment 1, other condition is constant, DASA diazonium liquid is joined in the conjugates the former powder 89.5g of gained, product signature 89.7g.Chromatic light deviation Δ A is 0.758, and product coloured light is red partially.
Embodiment 4:
In embodiment 1, the diazotization mode of PNA is adjusted into and adds hydrochloric acid making beating 1h earlier, and is on the rocks then, add Sodium Nitrite diazonium, and the diazonium mode of DASA also is that so other condition is with embodiment 1, and gained result and embodiment 1 are much at one.
Experimental example
Embodiment 1 gained sample is dyed sample use fabric: polyamide fibre 1g, colourity 1.5%, bath raio 1:50, acetic acid 1%, Sodium sulfate anhydrous.min(99) 10%.Pipette dye liquor 30ml in beaker, add 1% acetic acid 1ml, 10% Sodium sulfate anhydrous.min(99) 10ml, adding distil water stirs evenly to 50ml.In 40 ℃ of dye baths that drop into preparation, 50mim is warming up to 90 ℃, keeps 45min with fabric, and cooling is taken out, and washing is dried, and measuring its application performance is degree of exhaustion 98%, 5 grades of light fastness, soaping fastness (40 ℃) the 4-5 level of fading, staining 4-5 level.
Comparative example 1:
Recover original technology: adding 100g water in the 250ml flask, open and stir, add 20.0g86%H acid, making beating 0.5h, adding 7.5g30% liquid caustic soda is molten entirely to H acid, transfers pH=7.3.In another 250ml flask, add 50g water, 8.2g 99% p-Nitroaniline, the making beating back adds the 50g trash ice, be cooled to 0-5 ℃, add 30g31% hydrochloric acid then, control 0-5 ℃, treat the disposable adding 4.5g97% Sodium Nitrite in the complete molten back of PNA, keep and add the 0.6g thionamic acid behind the reaction 1h and make PNA diazonium liquid.
Above-mentioned PNA diazonium liquid is joined dissolved H acid solution, and the ice-water bath controlled temperature is below 5 ℃, and pH value reaction 15h finishes a coupled reaction
The DASA that in another 500ml flask, adds 80g water and 13.5g folding hundred, making beating also adds 75g trash ice and 42g 30% hydrochloric acid, and when temperature was reduced to 2-3 ℃, disposable adding 10g Sodium Nitrite (being made into 20% aqueous solution) kept stirring reaction 1h below 5 ℃.Add the 0.8g thionamic acid again and obtain DASA diazonium liquid.
DASA diazonium liquid is joined in the coupling material, and reinforced finishing then adds about 15g 30% liquid caustic soda and transfers pH=7.5-8.5.Holding temperature 5-8 ℃ of reaction 4h finishes two coupled reactions.Add 7.2gMPD (being made into the aqueous solution with 25g hot water and 1.2g liquid caustic soda) in above-mentioned secondary coupled reaction thing, reinforced finishing answering 3h to get three conjugates below 10 ℃.
The gained material is heated to 85-90 ℃, adds refined salt 30g analysis of material, is cooled to 25 ℃ of filtrations, filter cake 200g5% salt water rinse, oven dry, pulverizing, and sample signature product 82g, coloured light is close.
Comparative example 2:
Condensation part is with comparative example 1, and FF adopts does not saltout but the direct method of sabot oven dry, and the Δ C that draws a design as a result is dark partially 1.62, aberration Δ E 1.44.
Comparative example 3:
Compare with embodiment 1, appropriate change charging capacity ratio is kept to 15.30g with the DASA consumption from 15.69g, and other consumptions and condition are constant, and the result that draws a design green partially 0.472.
Claims (8)
1. production method suc as formula the matching stain of (III), its production is characterised in that and comprises the steps:
(1) p-Nitroaniline diazonium salt and H acid are carried out first time coupled reaction and are obtained formula (I) compound solution;
(2) DASA diazonium salt and formula (I) compound solution carries out second time coupled reaction and obtains formula (II) compound solution;
(3) mphenylenediamine and formula (II) compound solution carries out for the third time that coupled reaction obtains formula (III) compound magma;
(4) formula (III) compound magma spraying drying is promptly got the former powder of formula (III) compound.
2. the production method of matching stain according to claim 1, it is characterized in that: the solid content of described formula (III) compound magma is 10-30%.
3. the production method of matching stain according to claim 2, it is characterized in that: the solid content of described formula (III) compound magma is 15-22%.
4. the production method of matching stain according to claim 1, it is characterized in that: the molar ratio of described raw material is p-Nitroaniline: H acid: the DASA diazonium salt: mphenylenediamine=1: 0.8-1.2: 0.8-1.2: 0.7-1.0.
5. the production method of matching stain according to claim 1 is characterized in that: the feed way of described three step coupled reactions are respectively: the H acid solution joins in the p-Nitroaniline diazonium salt solution, formula (I) compound solution joins in the DASA diazonium salt solution, mphenylenediamine joins in formula (II) compound solution with solid-state form.
6. the production method of matching stain according to claim 1 is characterized in that: the pH value of step (1) coupled reaction is 0.5-1.5, and the pH value of step (2) coupled reaction is 3.0-7.0, and the pH value of step (3) coupled reaction is 6.0-10.0.
7. the production method of matching stain according to claim 6 is characterized in that: the pH value of step (1) coupled reaction is 0.8-1.0, temperature of reaction 5-8 ℃, reaction times 5～10h; The pH value of step (2) coupled reaction is 4.5-5.5, temperature of reaction 5-8 ℃, and reaction times 2～5h; The pH value of step (3) coupled reaction is 6.0-7.0, temperature of reaction 5-8 ℃, and reaction times 1～3h.
8. production method according to claim 1, the color base purity that it is characterized in that described former powder are greater than 80%, and former powder power part is 150-180%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010216157XA CN101906258A (en) | 2010-06-30 | 2010-06-30 | Method for producing acid dye |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010216157XA CN101906258A (en) | 2010-06-30 | 2010-06-30 | Method for producing acid dye |
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| CN101906258A true CN101906258A (en) | 2010-12-08 |
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| CN201010216157XA Pending CN101906258A (en) | 2010-06-30 | 2010-06-30 | Method for producing acid dye |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660134A (en) * | 2012-05-10 | 2012-09-12 | 金华恒利康化工有限公司 | Acidic green-light black dye and preparation method thereof |
| CN102775813A (en) * | 2012-07-09 | 2012-11-14 | 天津市大邱庄宏达化工有限公司 | Pollution-free preparation process for acidic dye |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101040011A (en) * | 2004-10-08 | 2007-09-19 | 德意志戴斯达纺织品及染料两合公司 | Reactive polyazo dyes |
| CN101538414A (en) * | 2008-03-17 | 2009-09-23 | 天津三环化学有限公司 | Method for preparing acid black 172 |
| CN101580648A (en) * | 2009-05-04 | 2009-11-18 | 泰兴市锦鸡染料有限公司 | Reactive blue dye and preparation process thereof |
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2010
- 2010-06-30 CN CN201010216157XA patent/CN101906258A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101040011A (en) * | 2004-10-08 | 2007-09-19 | 德意志戴斯达纺织品及染料两合公司 | Reactive polyazo dyes |
| CN101538414A (en) * | 2008-03-17 | 2009-09-23 | 天津三环化学有限公司 | Method for preparing acid black 172 |
| CN101580648A (en) * | 2009-05-04 | 2009-11-18 | 泰兴市锦鸡染料有限公司 | Reactive blue dye and preparation process thereof |
Non-Patent Citations (2)
| Title |
|---|
| WU ZU-WANG ET AL.: "A Study on 4,4"-Diaminobenzene Sulfonanilide (DABSA) and the Properties of Dyes Derived from DABSA", 《CHEMICAL RESEARCH IN CHINESE UNIVERSITIES》 * |
| 章杰: "近年国内外精细化工行业使用的新型干燥器", 《染料工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660134A (en) * | 2012-05-10 | 2012-09-12 | 金华恒利康化工有限公司 | Acidic green-light black dye and preparation method thereof |
| CN102775813A (en) * | 2012-07-09 | 2012-11-14 | 天津市大邱庄宏达化工有限公司 | Pollution-free preparation process for acidic dye |
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Application publication date: 20101208 |