CN104327535A - Preparation method of acid black 172 - Google Patents
Preparation method of acid black 172 Download PDFInfo
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- CN104327535A CN104327535A CN201410539866.XA CN201410539866A CN104327535A CN 104327535 A CN104327535 A CN 104327535A CN 201410539866 A CN201410539866 A CN 201410539866A CN 104327535 A CN104327535 A CN 104327535A
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Abstract
The invention relates to a preparation method of acid black 172. The method comprises the following steps: 1, adding water to 6-nitro-1,2-diazoxynaphthalene-4-sulfonic acid to dissolve, adding a sodium hydroxide solution, and stirring; 2, adding sodium hydroxide into 2-naphthol, adding water, and carrying out stirring heating for dissolving; 3, rapidly putting the prepared 2-naphthol solution in the 6-nitro-1,2-diazoxynaphthalene-4-sulfonic acid solution, and coupling to obtain a coupling solution; and 4, adding chromium acetate to the coupling solution, heating the coupling solution to 100-102DEG C, and carrying out heat insulation stirring to obtain the finished acid black 172 slurry. The coupling temperature rises to 67-72DEG C, and chromium acetate is adopted as a complexing agent, so the coupling reaction rate and the complexing reaction rate are improved, the complexing cost is reduced, thereby the preparation method of the acid black 172 is environmentally-friendly.
Description
Technical field
The present invention relates to a kind of preparation method of 1:2 azo metal complex dyestuff, specifically a kind of preparation method of acid black 172.
Background technology
Acid black 172 is a kind of matching stain by the name of international dyestuff numbering, its trade name is neutral black S-RL, it has higher dyefastness to wool, tynex, dying operation simple application field widely, nearly 30,000 tons of annual market demand.
The principal reaction of current production acid black 172 is as follows:
1,6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid dissolves:
2, beta naphthal salify:
3, coupling:
4, complexing:
6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid mainly drops in dissolution kettle by the production method of above-mentioned reaction, adds water, and with in 30% liquid caustic soda and PH=5, neutralizer puts into coupled reaction still; Become in salt oven to add beta naphthal at beta naphthal, water, sheet alkali is warming up to 70 DEG C of salifies, this liquid is put into coupling still 40-45 DEG C to carry out adjusting PH to be that 5.8-6.0 adds basic chromium sulfate solution warms and within 2-4 hour, obtains acid black 172 slurries to 100-102 DEG C of reaction with formic acid after completion of the reaction, above-mentioned slurries filtration, spraying dry are obtained acid black 172 dye product.Although but aforesaid method obtains 172 products has following problem: (1) reaction yield is low, by product and impurity more, (2) acid black 172 product sun-proof, washing fastness lower (3) operating process are complicated.
Summary of the invention
The present invention is directed to the problems referred to above, a kind of preparation method of acid black 172 is provided, the steps include:
(1) 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel water stirring and dissolving, temperature control 5-20 DEG C, hydro-oxidation sodium solution is neutralized to PH=3.5-4, is prepared into 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid solutions;
(2) beta naphthal is dropped in dissolving vessel, adds water, hydro-oxidation sodium, stirring, rising temperature for dissolving salify;
(3) the solution mixing prepared by above-mentioned steps (1), (2), be 9-11 with the sodium hydroxide solution control pH of 25%-30% (m/m), coupled reaction is carried out in intensification stirring, obtains coupling solution;
(4) in above-mentioned coupling solution, add the chromium acetate aqueous solution, coupling solution is heated up, stir and carry out complex reaction, obtain acid black 172 slurries finished product.
Above-mentioned steps (1) described concentration of sodium hydroxide solution is 25%-30% (m/m); The temperature of the described dissolving salify of step (2) is 65-85 DEG C; The described coupled reaction temperature of step (3) is 67-72 DEG C, and reaction pH is 10-10.5, and the reaction times is 1h-3h; The described chromium acetate concentration of aqueous solution of step (4) is 40-60% (m/m), and complex reaction temperature is 100-102 DEG C, and the reaction times is 1h-4h; The feed molar ratio (mass ratio) of 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid, beta naphthal and chromium acetate is 10:5:4.
Production technique of the present invention is simple, reaction conditions controls scientific and reasonable, life cycle of the product is short, yield is high, quality is good, rub resistance, water-fastness, light fastness significantly improve, side reaction and impurity obviously reduce, and production cost is lower, production efficiency is higher, is a kind of preparation method of acid black 172 of more environmental protection.
Advantage of the present invention and beneficial effect are:
1, the preparation method of this acid black 172 has improvement in the control of coupled reaction temperature condition, and change 67-72 DEG C of product yield into by original coupled reaction temperature 40-45 DEG C and significantly improve, impurity and side reaction obviously reduce, and quality product is further enhanced.
2, the preparation method of this acid black 172 changes chromium acetate at complex reaction complexing agent into by basic chromium sulfate and reduces complexing cost, improves quality product.
3, production technique of the present invention is simple, and reaction conditions controls rationally, and good product quality, rub resistance, water-fastness, light fastness is high, side reaction and impurity few, and production cost is lower, is a kind of acid black 172 product processes of more environmental protection.
Embodiment
Embodiment 1
(1) take 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid 12.75 grams, add 40 grams of water stirring and dissolving, temperature control 20 DEG C drips in 30% (m/m) sodium hydroxide solution and PH=4, is prepared into 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid solutions;
(2) 6.5 grams of beta naphthals, 30 grams of water, 1.92g sodium hydroxide are warming up to 70 DEG C and dissolve salify;
(3) become by beta naphthal saline solution to add in 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid neutralizer, gained liquid pH is 10, heats up and carries out coupled reaction, temperature control 70 DEG C, reaction 2h,
(4) add 10 gram of 50% (m/m) chromium acetate aqueous solution and be warming up to 100 DEG C of complex reactions 1 hour, obtain acid black 172 slurries finished product, can be used for wool or tynex dyeing.
Embodiment 2
(1) take 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid 25.5 grams, add 80 grams of water stirring and dissolving, temperature control 15 DEG C drips in 20% (m/m) sodium hydroxide solution and PH=3.5, is prepared into 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid solutions;
(2) by 13 grams of beta naphthals, 60 grams of water, 3.84 grams of sodium hydroxide mixing, be warming up to 75 DEG C and dissolve salify;
(3) become by beta naphthal saline solution to add in 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid neutralizer, gained liquid pH is 9, heats up and carries out coupled reaction, temperature control 67 DEG C, reaction 2.5h,
(4) add 25 gram of 40% (m/m) chromium acetate aqueous solution and be warming up to 102 DEG C of complex reactions 1.5 hours, obtain acid black 172 slurries finished product, can be used for wool or tynex dyeing.
Embodiment 3
(1) get 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid 300kg, add 940kg water stirring and dissolving, temperature control 20 DEG C drips in 30% (m/m) sodium hydroxide solution and PH=4, is prepared into 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid solutions;
(2) 153kg (100%) beta naphthal, 700kg water, 47kg sodium hydroxide are warming up to 70 DEG C and dissolve salify;
(3) saline solution is become by beta naphthal to add coupling in 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid neutralizer, temperature control 70 DEG C, reaction 2h,
(4) add 235kg50% (m/m) the chromium acetate aqueous solution and be warming up to 100 DEG C of complex reactions 1 hour, obtain acid black 172 slurries finished product, can be used for wool or tynex dyeing.
Above-mentioned acid black 172 slurries are added 500kg sodium sulfate, spraying dry, obtains the acid black 172 product (standard No. is HG/T3888-2014, and chemical industry proposed standard name is called erie black NM-3BRL) that 1 ton of intensity is 100 points.
Comparative example:
(1) take 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid 445kg, add 1059kg water and stir, temperature control 20 DEG C drips in 30% (m/m) sodium hydroxide solution and PH=4;
(2) 225kg2-naphthols, 794kg water, 51kg sodium hydroxide are warming up to 70 DEG C and dissolve salify;
(3) saline solution is become by beta naphthal to add coupling in 6-nitro-1,2 diazoxy naphthalene-4-sulfonic acid neutralizer, temperature control 35 DEG C, reaction 2h.
(4) add 159kg99% (m/m) acetic acid, 191kg basic chromium sulfate, be warming up to 100 DEG C of complex reactions 1 hour, obtain acid black 172 product slurry.
Above-mentioned acid black 172 slurries are added 500kg sodium sulfate, spraying dry, obtains the acid black 172 product (standard No. is HG/T3888-2014, and chemical industry proposed standard name is called erie black NM-3BRL) that 1 ton of intensity is 100 points.
Claims (7)
1. a preparation method for acid black 172, is characterized in that: the complexing agent selected is chromium acetate; Concrete preparation process is as follows:
(1) 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel water stirring and dissolving, temperature control 5-20 DEG C, hydro-oxidation sodium solution is neutralized to PH=3.5-4, is prepared into 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid solutions;
(2) beta naphthal is dropped in dissolving vessel, adds water, hydro-oxidation sodium, intensification stirring and dissolving salify;
(3) the solution mixing prepared by above-mentioned steps (1), (2), coupled reaction is carried out in intensification stirring, obtains coupling solution;
(4) in above-mentioned coupling solution, add the chromium acetate aqueous solution, coupling solution is heated up, stir and carry out complex reaction, obtain acid black 172 slurries finished product.
2., by the preparation method of acid black 172 according to claim 1, it is characterized in that: step (1) described concentration of sodium hydroxide solution is 25%-30% (m/m).
3. by the preparation method of acid black 172 according to claim 1, it is characterized in that: in step (2), beta naphthal is 3-3.5:1 with sodium hydroxide addition ratio (m/m), and the temperature of described dissolving salify is 65-85 DEG C.
4., by the preparation method of acid black 172 according to claim 1, it is characterized in that: the described coupled reaction temperature of step (3) is 67-72 DEG C, and reaction pH is 9-11, and the reaction times is 1h-3h.
5., by the preparation method of acid black 172 according to claim 1, it is characterized in that: the described chromium acetate concentration of aqueous solution of step (4) is 40-60% (m/m).
6., by the preparation method of acid black 172 according to claim 1, it is characterized in that: the described complex reaction temperature of step (4) is 100-102 DEG C, and the reaction times is 1h-4h.
7., by the preparation method of acid black 172 according to claim 1, it is characterized in that: the feed molar ratio (mass ratio) of 6-nitro-1,2-diazoxy naphthalene-4-sulfonic acid, beta naphthal and chromium acetate is 10:5:4.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410539866.XA CN104327535A (en) | 2014-10-11 | 2014-10-11 | Preparation method of acid black 172 |
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| CN201410539866.XA CN104327535A (en) | 2014-10-11 | 2014-10-11 | Preparation method of acid black 172 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694524A (en) * | 2016-01-28 | 2016-06-22 | 江苏盛吉化工有限公司 | Preparation method of acid black 172 |
| CN111073336A (en) * | 2019-12-30 | 2020-04-28 | 浙江大学滨海产业技术研究院 | Preparation and application of high-strength acidic 172 black liquid dye |
| CN111171594A (en) * | 2019-12-31 | 2020-05-19 | 恒升化工有限公司 | Preparation method of metal complex dye with low residual chromium ions |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10304A (en) * | 1853-12-06 | evans | ||
| US4996303A (en) * | 1987-12-04 | 1991-02-26 | Ciba-Geigy Corporation | Preparation of 1:2 metal complex dyes by coupling in the presence of a metal donor in an inert gas atmosphere |
| US5196518A (en) * | 1987-09-08 | 1993-03-23 | Ciba-Geigy Corporation | Process for the preparation of metallizable azo dyes by carrying out the coupling in the presence of a buffer mixture |
| CN101538414A (en) * | 2008-03-17 | 2009-09-23 | 天津三环化学有限公司 | Method for preparing acid black 172 |
| CN101665628A (en) * | 2009-09-16 | 2010-03-10 | 大连理工大学 | Chrome complex dye as well as preparation method and applications thereof |
-
2014
- 2014-10-11 CN CN201410539866.XA patent/CN104327535A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10304A (en) * | 1853-12-06 | evans | ||
| US5196518A (en) * | 1987-09-08 | 1993-03-23 | Ciba-Geigy Corporation | Process for the preparation of metallizable azo dyes by carrying out the coupling in the presence of a buffer mixture |
| US4996303A (en) * | 1987-12-04 | 1991-02-26 | Ciba-Geigy Corporation | Preparation of 1:2 metal complex dyes by coupling in the presence of a metal donor in an inert gas atmosphere |
| CN101538414A (en) * | 2008-03-17 | 2009-09-23 | 天津三环化学有限公司 | Method for preparing acid black 172 |
| CN101665628A (en) * | 2009-09-16 | 2010-03-10 | 大连理工大学 | Chrome complex dye as well as preparation method and applications thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694524A (en) * | 2016-01-28 | 2016-06-22 | 江苏盛吉化工有限公司 | Preparation method of acid black 172 |
| CN105694524B (en) * | 2016-01-28 | 2019-09-20 | 江苏盛吉化工有限公司 | A kind of preparation method of acid black 172 |
| CN111073336A (en) * | 2019-12-30 | 2020-04-28 | 浙江大学滨海产业技术研究院 | Preparation and application of high-strength acidic 172 black liquid dye |
| CN111171594A (en) * | 2019-12-31 | 2020-05-19 | 恒升化工有限公司 | Preparation method of metal complex dye with low residual chromium ions |
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