CN101538414B - Method for preparing acid black 172 - Google Patents
Method for preparing acid black 172 Download PDFInfo
- Publication number
- CN101538414B CN101538414B CN2008100524552A CN200810052455A CN101538414B CN 101538414 B CN101538414 B CN 101538414B CN 2008100524552 A CN2008100524552 A CN 2008100524552A CN 200810052455 A CN200810052455 A CN 200810052455A CN 101538414 B CN101538414 B CN 101538414B
- Authority
- CN
- China
- Prior art keywords
- solution
- acid black
- preparation
- added
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 *c(cc1O*)c(cc(cc2)[N+]([O-])=O)c2c1N=C Chemical compound *c(cc1O*)c(cc(cc2)[N+]([O-])=O)c2c1N=C 0.000 description 3
Landscapes
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing acid black 172. The method comprises the following steps that: (1) 6-nitro-1 and 2-diazoxynaphthalene-4-sulfonic acid are put into a dissolution tank, added with water for dissolution, added with a sodium hydroxide solution and stirred. (2) 2-naphthol is put into the dissolution tank, added with water for dissolution, added with the sodium hydroxide solution, stirred, heated, added with a dispersant and aliphatic diol or ether and stirred again; (3) a prepared 2-naphthol solution is rapidly put into and coupled with a solution with 6-nitro-1 and2-diazoxynaphthalene-4-sulfonic acid so as to obtain coupled liquid; and (4) the coupled liquid is added with formic acid, ammonium bicarbonate or sodium bicarbonate and basic chromium sulfate, heated to be between 100 and 102 DEG C, thermally insulated and stirred so as to obtain an acid black 172 serous finished product. The method for preparing acid black 172 has the advantages of simple production process, scientific reasonable control on reaction conditions, short production cycle of produces, high yield, good quality, friction resistance, obviously raised fastness of resisting rinse and sunshine, obviously reduced side reaction and impurities, low production cost, high production efficiency and better environment-friendly property.
Description
Technical field
The invention belongs to the metal complex azo dye field, especially 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, and it is to wool, and tynex has the high dyeing fastness; And price is lower; In dye field, use very extensively, the demand in market becomes the trend that increases year by year, and the demand of estimating whole world this year reaches 30,000 tons.The principal reaction of producing acid black 172 at present is following:
1.6-nitro-1, the dissolving of 2-diazoxy naphthalene-4-sulfonic acid:
2.2-the dissolving of naphthols:
3. coupled reaction:
4. chromaking reaction:
The working method of above-mentioned reaction mainly is with 6-nitro-1, and 2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel, the liquid caustic soda dissolving with 30%; Liquid after the dissolving is put into the coupled reaction jar, under stirring condition, will pour in the coupled reaction jar with the beta naphthal solution after the liquid caustic soda dissolving and react; After coupled reaction finishes, use formic acid adjustment reaction solution to be slightly acidic, add basic chromium sulfate; 100-102 ℃ of chromaking 12 hours, be cooled to room temperature then, add sodium-chlor and Repone K and saltout; Filter, dry, pulverize and obtain the finished product.Though aforementioned production method can access acid black 172, still there is following problem: (1). complex manufacturing: after product reacts completely, step such as also need saltout; (2). life cycle of the product is long: mainly by the coupling time and the decision of chromaking time of reaction, general coupled reaction needs 8 hours, and the chromaking reaction needed just can reach reaction end in 12 hours, and the concentration of general reaction solution is hanged down and had only 8-10% very much; (3). product yield is lower, and side reaction and impurity are more; (4). the wear-resisting wiping of product, water-fastly wash, light fastness is lower; (5). production cost is higher, and production efficiency is lower; (6). the discharging of waste liquid amount is big, and environmental pollution is serious, and treatment cost is higher; Wherein mainly be to saltout to produce a large amount of saliferous waste water from dyestuff in the step, isolated dyestuff filter cake also will be dried operations such as pulverizing simultaneously.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art, provide that a kind of production technique is simple, reaction conditions control is scientific and reasonable, life cycle of the product is short and yield is high, wear-resisting wiping, water-fastly wash, light fastness is high, the preparation method of the acid black 172 of environmental protection.
The technical problem that the present invention solves realizes through following technical scheme:
A kind of preparation method of acid black 172, the step of its preparation method is:
(1). with 6-nitro-1; 2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel A and is added the water making beating; Under stirring condition, in the A jar, add concentration and be 30% sodium hydroxide solution the pH value of solution is controlled between the 4-6, and to control solution temperature simultaneously be 10-20 ℃;
(2). beta naphthal is put into dissolving vessel B add the water making beating; The concentration that in the B jar, adds beta naphthal weight 83.7% is 30% sodium hydroxide solution, stirs and is warming up to 75-85 ℃, after beta naphthal dissolves fully; Add dispersion agent and aliphatic diol or ether, stir;
(3). under stirring condition, the liquid among the dissolving vessel B is put into dissolving vessel A carry out coupling, the temperature of control mixed solution is 40-45 ℃, and the PH of control mixed solution is 11.0-11.5, reaction solution is stirred 1-2h obtain coupling solution;
(4). in coupling solution, add formic acid, control PH is 5.8-6.0, adds bicarbonate of ammonia or sodium hydrogencarbonate, adds basic chromium sulfate again, coupling solution is warming up to 100-102 ℃ is incubated and stirred 2-4 hour, obtains acid black 172 slurries finished product.
And, described 6-nitro-1, the weight ratio that 2-diazoxy naphthalene-4-sulfonic acid, beta naphthal and basic chromium sulfate add is 590: 302: 335.
And described dispersion agent is anionic dispersing agents or non-ionic dispersing agent, and its addition is the 1-5% of beta naphthal weight in the reaction system.
And described anionic dispersing agents is Dispersant MF or dispersion agent beta-naphthalenesulfonic-acid and formaldehyde condensation products or dispersing agent NNO and sodium lignosulfonate, and non-ionic dispersing agent is ethoxylated nonylphenol or ethoxylation unsaturated fatty acids.
And described aliphatic diol or ether are the wherein a kind of of terepthaloyl moietie, Ucar 35, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol monobutyl ether, and its addition is the 3-8% of beta naphthal weight in the reaction system.
And, with described acid black 172 slurries finished product spraying drying, promptly obtain dry product.
Advantage of the present invention and beneficial effect are:
1. added dispersion agent and aliphatic diol or ether among the preparation method of this acid black 172, the viscosity of coupled reaction is obviously reduced, the concentration of coupled reaction liquid is improved; Accelerated the probability of diazo component (6-nitro) and the intermolecular collision of coupling component (beta naphthal), speed of response is obviously accelerated, coupled reaction only needed to react completely in 1 hour now; Shortened 7 hours fully than coupling in original 8 hours, the chromaking reaction only needed get final product in 3 hours now, had shortened 9 hours than original 12 hours; The life cycle of the product cocondensation has been lacked 16 hours; Practice thrift a large amount of energy, reduced production cost, improved production efficiency.
2. the preparation method of this acid black 172 has had tangible improvement in the control of coupled reaction temperature condition; Change 40-45 ℃ into by 20-25 ℃ of original coupled reaction temperature; Coupled reaction speed is obviously accelerated; Product yield improves, and side reaction and impurity obviously reduce, and quality product is further improved.
3. the preparation method of this acid black 172 is in the chromaking reaction process, the H that emits when adding in a spot of bicarbonate of ammonia or the sodium hydrogencarbonate with the chromaking reaction
+, the chromaking speed of response is obviously accelerated, and product slurry concentration is increased to 25-30% by original 8-10%; Production efficiency is significantly improved, and has realized spraying drying, has saved salting-out procedures; Practiced thrift a large amount of Repone K and sodium-chlor, avoided of the pollution of saliferous dyestuff waste liquid, protected environment environment; Reduce treatment cost, improved economic benefit.
4. production technique of the present invention is simple; Reaction conditions control is scientific and reasonable; Life cycle of the product is short, yield is high, good, the wear-resisting wiping of quality, water-fastly wash, light fastness is high, 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.
Embodiment
The present invention further details through following examples.Need to prove: following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Embodiment 1
A kind of preparation method of acid black 172, wherein this preparing method's step is:
(1). with the 6-nitro-1 of 295g100%; 2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel A and is added the 1000ml water dissolution; Under stirring condition; In the A jar, adding concentration and be 30% sodium hydroxide solution is 5 with the control pH value, and to control solution temperature simultaneously be 18 ℃, and the method for specifically controlling the solution cooling can adopt mode on the rocks;
(2). the 151g2-naphthols is put into dissolving vessel B add the 400ml water dissolution; Adding 95ml concentration is 30% sodium hydroxide solution in the B jar; Stirring is warming up to 80 ℃; After beta naphthal dissolves fully, add 3g dispersion agent NSO (beta-naphthalenesulfonic-acid and formaldehyde condensation products) and 8g ethylene glycol monobutyl ether, stir;
(3). under quick stirring condition, the liquid among the dissolving vessel B poured into rapidly among the dissolving vessel A form mixed solution, the temperature of control mixed solution is 40 ℃, and the PH of control mixed solution is 11.0, mixed solution is stirred 1h obtain coupling solution;
(4). in coupling solution, add 90g formic acid, control PH is 5.8, adds the 20g sodium hydrogencarbonate; Add the 167.5g basic chromium sulfate again; Coupling solution was warming up to 100 ℃ of insulated and stirred 3 hours, and obtaining solid content is the acid black 172 slurries finished product of 25-30%, is used for the dyeing of wool or tynex.
With above-mentioned acid black 172 slurries finished product spraying drying, obtain dry product.
Embodiment 2
A kind of preparation method of acid black 172, wherein this preparing method's step is:
(1). with the 6-nitro-1 of concentration 295g100%; 2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel A and is added the 1000ml water dissolution; Under stirring condition, adding concentration is 30% sodium hydroxide solution in the A jar, and the control pH value is 4; And to control solution temperature simultaneously be 20 ℃, and the method for specifically controlling the solution cooling can adopt mode on the rocks;
(2). the 151g2-naphthols is put into dissolving vessel B add the 400ml water dissolution; Adding 95ml concentration is 30% sodium hydroxide solution in the B jar, stirs and is warming up to 85 ℃, after beta naphthal dissolves fully; Add 3g dispersion agent ethoxylated nonylphenol and 8g Ucar 35, stir;
(3). under quick stirring condition, the liquid among the dissolving vessel B poured into rapidly among the dissolving vessel A form mixed solution, the temperature of control mixed solution is 45 ℃, and the PH of control mixed solution is 11.5, mixed solution is stirred 2h obtain coupling solution;
(4). in coupling solution, add 90g formic acid, control PH is 6, adds 20g bicarbonate of ammonia; Add the 167.5g basic chromium sulfate again; Coupling solution was warming up to 102 ℃ of insulated and stirred 4 hours, and obtaining solid content is the acid black 172 slurries finished product of 25-30%, is used for the dyeing of wool or tynex.
With above-mentioned acid black 172 slurries finished product spraying drying, obtain dry product.
Embodiment 3
A kind of preparation method of acid black 172, wherein this preparing method's step is:
(1). with the 6-nitro-1 of concentration 295g100%; 2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel A and is added the 1000ml water dissolution; Under stirring condition, adding concentration is 30% sodium hydroxide solution in the A jar, and the control pH value is 6; And to control solution temperature simultaneously be 12 ℃, and the method for specifically controlling the solution cooling can adopt mode on the rocks;
(2). the 151g2-naphthols is put into dissolving vessel B add the 400ml water dissolution; Adding 95ml concentration is 30% sodium hydroxide solution in the B jar, stirs and is warming up to 75 ℃, after beta naphthal dissolves fully; Add 3g dispersion agent sodium lignosulfonate and 8g ethylene glycol monomethyl ether, stir;
(3). under quick stirring condition, the liquid among the dissolving vessel B poured into rapidly among the dissolving vessel A form mixed solution, the temperature of control mixed solution is 43 ℃, and the PH of control mixed solution is 11.3, mixed solution is stirred 1.5h obtain coupling solution;
(4). in coupling solution, add 90g formic acid, control PH is 5.9, adds 20g bicarbonate of ammonia; Add the 167.5g basic chromium sulfate again; Coupling solution was warming up to 101 ℃ of insulated and stirred 2.5 hours, and obtaining solid content is the acid black 172 slurries finished product of 25-30%, is used for the dyeing of wool or tynex.
With above-mentioned acid black 172 slurries finished product spraying drying, obtain dry product.
In addition, the dispersion agent that the embodiment of the invention adopted can also adopt Dispersant MF or dispersing agent NNO or ethoxylation unsaturated fatty acids except above-mentioned points.
Aliphatic dialcohol that the embodiment of the invention adopted or ether can also adopt terepthaloyl moietie, ethylene glycol monoethyl ether except above-mentioned points.
Claims (6)
1. the preparation method of an acid black 172, it is characterized in that: the step of its preparation method is:
(1). with 6-nitro-1; 2-diazoxy naphthalene-4-sulfonic acid is put into dissolving vessel A and is added the water making beating; Under stirring condition, in the A jar, add concentration and be 30% sodium hydroxide solution the pH value of solution is controlled between the 4-6, and to control solution temperature simultaneously be 10-20 ℃;
(2). beta naphthal is put into dissolving vessel B add the water making beating; The concentration that in the B jar, adds beta naphthal weight 83.7% is 30% sodium hydroxide solution, stirs and is warming up to 75-85 ℃, after beta naphthal dissolves fully; Add dispersion agent and aliphatic diol or ether, stir;
(3). under stirring condition, the liquid among the dissolving vessel B is put into dissolving vessel A carry out coupling, the temperature of control mixed solution is 40-45 ℃, and the pH of control mixed solution is 11.0-11.5, reaction solution is stirred 1-2h obtain coupling solution;
(4). in coupling solution, add formic acid, control pH is 5.8-6.0, adds bicarbonate of ammonia or sodium hydrogencarbonate, adds basic chromium sulfate again, coupling solution is warming up to 100-102 ℃ is incubated and stirred 2-4 hour, obtains acid black 172 slurries finished product.
2. the preparation method of acid black 172 according to claim 1 is characterized in that: described 6-nitro-1, the weight ratio that 2-diazoxy naphthalene-4-sulfonic acid, beta naphthal and basic chromium sulfate add is 590: 302: 335.
3. the preparation method of acid black 172 according to claim 1, it is characterized in that: described dispersion agent is anionic dispersing agents or non-ionic dispersing agent, its addition is the 1-5% of beta naphthal weight in the reaction system.
4. the preparation method of acid black 172 according to claim 3; It is characterized in that: described anionic dispersing agents is Dispersant MF or dispersing agent NNO and sodium lignosulfonate, and non-ionic dispersing agent is ethoxylated nonylphenol or ethoxylation unsaturated fatty acids.
5. the preparation method of acid black 172 according to claim 1; It is characterized in that: described aliphatic diol or ether are the wherein a kind of of terepthaloyl moietie, Ucar 35, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol monobutyl ether, and its addition is the 3-8% of beta naphthal weight in the reaction system.
6. the preparation method of acid black 172 according to claim 1 is characterized in that: with described acid black 172 slurries finished product spraying drying, promptly obtain dry product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100524552A CN101538414B (en) | 2008-03-17 | 2008-03-17 | Method for preparing acid black 172 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100524552A CN101538414B (en) | 2008-03-17 | 2008-03-17 | Method for preparing acid black 172 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101538414A CN101538414A (en) | 2009-09-23 |
| CN101538414B true CN101538414B (en) | 2012-07-04 |
Family
ID=41121812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100524552A Expired - Fee Related CN101538414B (en) | 2008-03-17 | 2008-03-17 | Method for preparing acid black 172 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101538414B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906258A (en) * | 2010-06-30 | 2010-12-08 | 杭州下沙恒升化工有限公司 | Method for producing acid dye |
| CN103044950B (en) * | 2013-01-24 | 2014-06-11 | 天津三环化学有限公司 | Method for producing acidic black 172 by using industrial waste chromium slag |
| CN103756362B (en) * | 2013-12-28 | 2015-09-02 | 浙江龙盛染料化工有限公司 | A kind of acid black dye composition |
| CN104194382B (en) * | 2014-09-04 | 2016-07-20 | 恒升化工有限公司 | A kind of preparation method of azo-type acid stain |
| CN104327535A (en) * | 2014-10-11 | 2015-02-04 | 辽宁精化科技有限公司 | 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 |
| CN109370256B (en) * | 2018-11-20 | 2020-06-26 | 恒升化工有限公司 | Mixed black dye and preparation method thereof |
| CN111073336B (en) * | 2019-12-30 | 2021-06-08 | 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5376151A (en) * | 1993-04-16 | 1994-12-27 | North Carolina State University | Environmentally friendly method for producing lightfast black shades on natural and synthetic substrates |
-
2008
- 2008-03-17 CN CN2008100524552A patent/CN101538414B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5376151A (en) * | 1993-04-16 | 1994-12-27 | North Carolina State University | Environmentally friendly method for producing lightfast black shades on natural and synthetic substrates |
Non-Patent Citations (3)
| Title |
|---|
| 任再新等.液状酸性染料的制备方法和检测.《染料与染色》.2006,第43卷(第5期),3-6. * |
| 杨新纬等.酸性染料发展概况.《丝绸》.1997,(第12期),55-58. * |
| 苏琼等.100%和98%硫酸对酸性媒介黑T质量影响的对比研究.《上海化工》.1999,第24卷(第6期),21-22、30. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101538414A (en) | 2009-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101538414B (en) | Method for preparing acid black 172 | |
| CN105694524B (en) | A kind of preparation method of acid black 172 | |
| CN103628330B (en) | A kind of environment-friendly liquid ciba blue 2b dyestuff compound adds auxiliary agent and preparation method thereof | |
| CN103964731B (en) | A kind of polycarboxylate water-reducer and preparation method thereof | |
| CN102585546A (en) | Preparation method for C.I. pigment red 53:1 | |
| CN110499218A (en) | A kind of efficient and environment-friendly type acid scouring agent and preparation method thereof | |
| CN103265821B (en) | High-covering power one-step production process of permanent bordeaux F5RK | |
| CN104831562A (en) | Hydroxypropyl carboxymethyl waxy corn starch acid dye printing paste and preparation method | |
| CN103773059A (en) | Preparation method of C.I.14 pigment yellow 2GSRW | |
| CN103397539A (en) | Reactive dye accelerant and preparation method for same | |
| CN103924456B (en) | A kind of production technology of reactive printing thickener | |
| CN101880465B (en) | Production method for acid dye finished product | |
| CN110183324B (en) | Preparation process of stearate | |
| CN104327535A (en) | Preparation method of acid black 172 | |
| CN102383319A (en) | Deepening agent and preparation method thereof | |
| CN103773077A (en) | Preparation method of solvent treatment covering type P.Y.83HR-70-RW | |
| CN101173110A (en) | Method for producing reduction olive T(C.I. Vat Biack 25) | |
| CN105541672B (en) | A kind of process for cleanly preparing of dye dispersant MF | |
| CN106590015A (en) | Direct orange S dye preparation process | |
| CN111004362B (en) | Preparation method of naphthalene-based superplasticizer | |
| CN103351645A (en) | Reactive blue dye and preparation method thereof | |
| CN105733292A (en) | Preparation method of acid black ACE | |
| CN102454120A (en) | Technology for rapidly dyeing polyester fiber cloth by using dispersible dye microcapsules | |
| CN104877368A (en) | Chrysophenine G production process | |
| CN105133030A (en) | Long-acting silicon wafer texture-etchant and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120704 Termination date: 20180317 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |