CN105418453A - Process for diazotizing azo-dye intermediate - Google Patents
Process for diazotizing azo-dye intermediate Download PDFInfo
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- CN105418453A CN105418453A CN201510866795.9A CN201510866795A CN105418453A CN 105418453 A CN105418453 A CN 105418453A CN 201510866795 A CN201510866795 A CN 201510866795A CN 105418453 A CN105418453 A CN 105418453A
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- sulfuric acid
- diazotization
- azoic dyestuff
- aromatic amine
- amine compounds
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- 0 CCCC=C(*)C=CC(C)(C)N Chemical compound CCCC=C(*)C=CC(C)(C)N 0.000 description 4
- OQLNCJJUUMYBOR-UHFFFAOYSA-O CC(CC#CC(C=C1C)[IH]#[O]C)=C1[NH3+] Chemical compound CC(CC#CC(C=C1C)[IH]#[O]C)=C1[NH3+] OQLNCJJUUMYBOR-UHFFFAOYSA-O 0.000 description 1
- QFMJFXFXQAFGBO-UHFFFAOYSA-O COc(cc1)cc([N+]([O-])=O)c1[NH3+] Chemical compound COc(cc1)cc([N+]([O-])=O)c1[NH3+] QFMJFXFXQAFGBO-UHFFFAOYSA-O 0.000 description 1
- JRQYXMFMRWWXDD-SNVBAGLBSA-N C[C@](C1)(C=C2)C1=CC(N=O)=C2NC Chemical compound C[C@](C1)(C=C2)C1=CC(N=O)=C2NC JRQYXMFMRWWXDD-SNVBAGLBSA-N 0.000 description 1
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Abstract
The invention discloses a novel method for a diazotizing process of disperse azo dye. The method comprises the following steps: (1) putting a compound into a reactor filled with water, and adding a small amount of ice to pulp; (2) adding sulfuric acid to keep on dissolving and pulping to sufficiently disperse the compound to facilitate the reaction; (3) adding ice to reduce the temperature to be lower than 5 DEG C; and (4) dropwise adding nitrosyl sulfuric acid for diazotizing, and reacting to the terminal point after the nitrosyl sulfuric acid is completely added. The novel diazotizing process has the advantages that: (1) sodium nitrite or hydrochloric acid is not used in diazotization, so that sodium ions or chloride ions are not introduced, and post-treatment of wastewater can be facilitated; (2) waste sulfuric acid which is generated in production, has a concentration of 5-30 percent and is difficult to treat can be used as the added sulfuric acid; and (3) the compound for diazotizing can be dry or wet, so that the energy consumption and wastewater in compound production can be reduced.
Description
Technical field
The invention belongs to dispersed dye preparation field, be specifically related to a kind of diazotization process of azoic dyestuff intermediate.
Background technology
Diazotization reaction prepares the first step of azoic dyestuff, mainly contains two kinds of reaction process at present, and one is hydrochloric acid heavy nitrogen, and one is sulfuric acid heavy nitrogen.
Hydrochloric acid heavy nitrogen is in hydrochloric acid medium, adds the Sodium Nitrite dissolved under cryogenic, and its reaction equation is:
The advantage of this method is that to carry out diazotizing compound can be wet product also can be dry product.Shortcoming will add hydrochloric acid and Sodium Nitrite in reaction process, introduces a large amount of chlorions and sodium ion.In follow-up wastewater treatment, these two kinds of ions are difficult to remove by simple method, are unfavorable for the requirement of environmental protection.
Sulfuric acid heavy nitrogen is under the condition of anhydrous or a small amount of water, and added by compound in the mixed solution of sulfuric acid and nitrosyl sulfuric acid and carry out diazotization, its reaction equation is:
The advantage of this method is carrying out not having chlorion and sodium ion in diazotizing process, only containing sulfuric acid in the waste water produced, is beneficial to the subsequent disposal of waste water in coupled processes; Shortcoming wants to want anhydrous in diazotizing compound or can only contain a small amount of water, and the compound produced like this will carry out processed, not only increase and manufacture a finished product, and also can cause the waste of industrial resources simultaneously, not meet the requirement of energy-saving and emission-reduction.
Publication number is the dilute sulphuric acid diazotization process that the Chinese patent application of CN103613511A discloses a kind of substituted aniline, it is in the dilute sulphuric acid of 40 ~ 95% that substituted aniline is added to mass percent by this diazotization process, nitrosyl sulfuric acid solution is added at the temperature of 0 ~ 40 DEG C, and keep 1 ~ 3 hour at this temperature, i.e. the diazotised compounds of obtained substituted aniline.The dilute sulphuric acid concentration that this preparation method uses is minimum can be low to moderate 40%, but after concentration reduces further, reaction effect can significantly reduce.
Summary of the invention
The invention provides a kind of diazotization process of azoic dyestuff intermediate, this diazotization process can react by the lower dilute sulphuric acid of working concentration, though working concentration be low to moderate 5% dilute sulphuric acid as reaction reagent time, still there is good reaction effect.
A diazotization process for azoic dyestuff intermediate, comprises the following steps: under the effect of dilute sulphuric acid and nitrosyl sulfuric acid, aromatic amine compounds carries out diazotization reaction, after reaction terminates, obtains diazo liquid through aftertreatment; Wherein, the concentration of described dilute sulphuric acid is 5 ~ 30%;
The temperature of described diazotization reaction controls between 0 ~ 5 DEG C.
The present inventor finds, if be reduced to a certain degree by the concentration of dilute sulphuric acid, then the direct method according to CN103613511A carries out diazotization reaction, and decomposition product is serious; And by the strict temperature of reaction that controls between 0 ~ 5 DEG C, the decomposition of raw material and product can be restrained effectively, the diazonium salt that can obtain with higher productive rate.
In DYE PRODUCTION, often can produce the lower dilute sulphuric acid of various concentration, because technical scheme of the present invention goes for the lower dilute sulphuric acid of concentration, as preferably, described dilute sulphuric acid comes from the Waste Sulfuric Acid produced in DYE PRODUCTION.
In the present invention, the consumption of described dilute sulphuric acid is equivalent or excessive a little, and as preferably, described dilute sulphuric acid and the mol ratio of aromatic amine compounds are 1.0 ~ 1.2:1.
In the present invention, the mass percent concentration of described nitrosyl sulfuric acid is 28 ~ 40%; Be preferably the nitrosyl sulfuric acid of 40%.
As preferably, described nitrosyl sulfuric acid and the mol ratio of aromatic amine compounds are 1.02 ~ 1.1:1.
As preferably, described aromatic amine compounds is selected from the one in following compound:
when adopting these raw materials, reaction effect is better.
In the present invention, described aromatic amine compounds can adopt dry product or wet product, and reaction effect is all better, and as preferably, described aromatic amine compounds directly adopts wet product, now, does not need to process especially arylamine class raw material.
Diazotization process of the present invention, specifically comprises the following steps:
(1) described aromatic amine compounds is pulled an oar in water, on the rocksly in pulping process carry out grinding distribution, then add dilute sulphuric acid and continue making beating and obtain dispersion liquid;
(2) obtain throwing ice cooling in dispersion liquid to step (1), cool the temperature to less than 5 DEG C, start to add nitrosyl sulfuric acid, in adition process, the temperature of the hierarchy of control is no more than 5 DEG C, adds rear reaction and obtains described diazo liquid to terminal.
Compared with the existing technology, diazotisation methods of the present invention does not introduce chlorion and sodium ion, and requirement need not be had to the moisture content in aromatic amine compounds, dry product can be adopted also can to use wet product, the sulfuric acid adopted is the unmanageable Waste Sulfuric Acid produced in industrial production, under the prerequisite obtaining same quality product, the waste water producing dispersion dyes monomer generation is more prone to process, the production clean environment firendly more of compound, when environmental protection pressure strengthens day by day, novel process proposed by the invention more can meet the requirement that dye chemical industry is produced.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but protection scope of the present invention is not limited in this:
Embodiment 1
The wet product ortho-chlor-para nitraniline (water content accounts for 70% of gross weight) of 17.25g after adding end water 50g and give money as a gift in beaker, start stirring to pulp, pull an oar 50g on the rocks after 10 minutes, continue half an hour of pulling an oar, then add 9.8g sulfuric acid (mass percent concentration is 45%) after folding hundred, continue to stir half an hour, on the rocks cool to 0 DEG C after, start the nitrosyl sulfuric acid adding 33.3g40%, half an hour joining day.After nitrosyl sulfuric acid finishes, control temperature, below 5 DEG C, is incubated 1 hour, checks terminal, after terminal arrives, and diazo liquid and the coupling of the N got ready, N-dicyanoethyl-aniline.During coupling, first N, N-dicyanoethyl-aniline is dropped in coupling pot through grinding machine, then by ready-made diazo liquid press-in coupling pot, press rear insulation reaction to terminal.After coupled reaction terminates, intensification, suction filtration, be washed to neutrality, obtain C.I. DISPERSE ORANGE 30 200 44, the purity of gained filter cake reaches 94% after testing, and yield reaches 95%.
Comparative example 1
The wet product ortho-chlor-para nitraniline (water content accounts for 75% of gross weight) of 17.25g after adding end water 50g and give money as a gift in beaker, start stirring to pulp, pull an oar 50g on the rocks after 10 minutes, continue half an hour of pulling an oar, then the rear 9.8g sulfuric acid (mass percent concentration is 70%) of folding hundred is added, continue to stir half an hour, start the nitrosyl sulfuric acid adding 33.3g40%, half an hour joining day.Add in the process of nitrosyl sulfuric acid, do not control the temperature in reactor, allow it naturally heat up, by ready-made diazo liquid and the N that gets ready, the coupling of N-dicyanoethyl-aniline, after coupled reaction terminates, intensification, suction filtration, is washed to neutrality.Detected by the dyestuff obtained, its purity is 56%, and yield is 60%, and by product is mainly does not have diazotizing p-Nitroaniline and diazosoplit.
Embodiment 2
The wet product ortho-chlor-para nitraniline (water content accounts for 75% of gross weight) of 17.25g after adding end water 50g and give money as a gift in beaker, start stirring to pulp, pull an oar and add a small amount of ice 100g after 10 minutes, continue half an hour of pulling an oar, then add 9.8g sulfuric acid (mass percent concentration is 25%) after folding hundred, continue to stir half an hour, on the rocks cool to 0 DEG C after, start the nitrosyl sulfuric acid adding 33.3g40%, half an hour joining day.After nitrosyl sulfuric acid finishes, control temperature, below 5 DEG C, is incubated 1 hour, checks terminal, after terminal arrives, diazo liquid and the coupling of the N got ready, N-diacetyl oxy ethyl m-acetamidoaniline, after coupled reaction terminates, suction filtration, be washed to neutrality, obtain C.I. Red 167: 1, filter cake purity has 84% after testing, and yield reaches 88%.
Comparative example 2
The wet product ortho-chlor-para nitraniline (water content accounts for 70% of gross weight) of 17.25g after adding end water 50g and give money as a gift in beaker, start stirring to pulp, pull an oar and add a small amount of ice 100g after 10 minutes, continue half an hour of pulling an oar, then the rear 9.8g sulfuric acid (mass percent concentration is 80%) of folding hundred is added, continue to stir half an hour, start the nitrosyl sulfuric acid adding 33.3g40%, half an hour joining day.Add in the process of nitrosyl sulfuric acid, do not control the temperature in reactor, allow it naturally heat up, by ready-made diazo liquid and the N that gets ready, the coupling of N-diacetyl oxy ethyl m-acetamidoaniline, after coupled reaction terminates, intensification, suction filtration, is washed to neutrality.Detected by the dyestuff obtained, its purity is 50%, and yield is 55%, and by product is mainly does not have diazotizing ortho-chlor-para nitraniline and diazosoplit.
Embodiment 3
The wet product p-Nitroaniline (water content accounts for 5% of gross weight) of 13.8g after adding end water 100g and give money as a gift in beaker, start stirring to pulp, pull an oar and add a small amount of ice 50g after 10 minutes, continue half an hour of pulling an oar, then add 9.8g sulfuric acid (mass percent concentration is 30%) after folding hundred, continue to stir half an hour, on the rocks cool to 0 DEG C after, start the nitrosyl sulfuric acid adding 33.3g40%, 10 minutes joining days.After nitrosyl sulfuric acid finishes, control temperature is below 5 DEG C, be incubated 1 hour, check terminal, after terminal arrives, diazo liquid and the N-ethyl-N-cyanoethyl aniline coupling got ready, after coupled reaction terminates, intensification, suction filtration, be washed to neutrality, obtain C.I. Disperse Red 25, detect its purity and have 96%, yield is 95%.
Comparative example 3
The wet product p-Nitroaniline (water content accounts for 5% of gross weight) of 13.8g after adding end water 100g and give money as a gift in beaker, start stirring to pulp, pull an oar and add a small amount of ice 50g after 10 minutes, continue half an hour of pulling an oar, then the rear 9.8g sulfuric acid (mass percent concentration is 30%) of folding hundred is added, continue to stir half an hour, start the nitrosyl sulfuric acid adding 33.3g40%, 10 minutes joining days.Add in the process of nitrosyl sulfuric acid, do not control the temperature in reactor, allow it naturally heat up, by ready-made diazo liquid and the N-ethyl-N-cyanoethyl aniline coupling got ready, after coupled reaction terminates, intensification, suction filtration, be washed to neutrality.Detected by the dyestuff obtained, purity is 45%, and yield is 50%, and the inside has much does not have diazotizing p-Nitroaniline and diazosoplit.
The couling process of embodiments of the invention and comparative example is as follows:
In coupling still, add end water, ice, add sulfuric acid, control temperature about 0 ~ 10 DEG C, drop into corresponding coupling component, weight of material is than being (end water+ice): sulfuric acid: coupling component=13:1:1, after stirring, slow dropping diazo component, whole process control temp 0 ~ 10 DEG C, after adding, detect qualified after, control coupling acid number 8%, be warmed up to 50 DEG C, filter, after washing neutrality, obtain product.
The dyestuff of embodiment 1 ~ 3 is pressed GB/T2394 respectively, GB/T540, GB/T3921, GB/T5718, GB/T3920 and GB/T2397 measures the coloured light intensity of dyestuff, dispersed, washing fastness, fastness to sublimation, resistance to dry fastness and lifting force, and the stable like products its result and Workshop Production gone out compares, net result shows: after using method of the present invention to carry out diazotization, carry out each performance index of dyestuff that coupling obtains almost consistent with the product that traditional technology obtains, but waste water more easily processes, more meet energy-saving and emission-reduction, the requirement of green chemical industry.
Claims (8)
1. a diazotization process for azoic dyestuff intermediate, comprises the following steps: under the effect of dilute sulphuric acid and nitrosyl sulfuric acid, aromatic amine compounds carries out diazotization reaction, after reaction terminates, obtains diazo liquid through aftertreatment; It is characterized in that, the concentration of described dilute sulphuric acid is 5 ~ 30%;
The temperature of described diazotization reaction controls between 0 ~ 5 DEG C.
2. the diazotization process of azoic dyestuff intermediate according to claim 1, is characterized in that, described dilute sulphuric acid comes from the Waste Sulfuric Acid that produces in DYE PRODUCTION or the vitriol oil after dilution.
3. the diazotization process of azoic dyestuff intermediate according to claim 1, is characterized in that, described dilute sulphuric acid and the mol ratio of aromatic amine compounds are 1.0 ~ 1.2:1.
4. the diazotization process of azoic dyestuff intermediate according to claim 1, is characterized in that, the mass percent concentration of described nitrosyl sulfuric acid is 28 ~ 40%.
5. the diazotization process of azoic dyestuff intermediate according to claim 1, is characterized in that, described nitrosyl sulfuric acid and the mol ratio of aromatic amine compounds are 1.02 ~ 1.1:1.
6. the diazotization process of azoic dyestuff intermediate according to claim 1, is characterized in that, described aromatic amine compounds is selected from the one in following compound:
7. the diazotization process of azoic dyestuff intermediate according to claim 1, is characterized in that, described aromatic amine compounds directly adopts wet product.
8. the diazotization process of azoic dyestuff intermediate according to claim 1, is characterized in that, comprise the following steps:
(1) described aromatic amine compounds is pulled an oar in water, on the rocksly in pulping process carry out grinding distribution, then add dilute sulphuric acid and continue making beating and obtain dispersion liquid;
(2) obtain throwing ice cooling in dispersion liquid to step (1), cool the temperature to less than 5 DEG C, start to add nitrosyl sulfuric acid, in adition process, the temperature of the hierarchy of control is no more than 5 DEG C, adds rear reaction and obtains described diazo liquid to terminal.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187814A (en) * | 2016-06-29 | 2016-12-07 | 浙江闰土研究院有限公司 | A kind of synthetic method of disperse dyes diazol |
| CN108929244A (en) * | 2018-08-07 | 2018-12-04 | 江苏之江化工有限公司 | A kind of diazonium method of tide product nitrobenzene amine |
| CN111018806A (en) * | 2019-12-25 | 2020-04-17 | 安道麦安邦(江苏)有限公司 | Method and device for continuously preparing 5-amino-1, 2, 3-thiadiazole |
| CN115353751A (en) * | 2022-08-26 | 2022-11-18 | 浙江闰土染料有限公司 | Preparation method of monoazo disperse dye |
| CN116814089A (en) * | 2023-02-01 | 2023-09-29 | 山东安诺其精细化工有限公司 | Process for synthesizing disperse dye and disperse dye |
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| CN103232409A (en) * | 2012-12-31 | 2013-08-07 | 上海安诺其纺织化工股份有限公司 | Preparation method of disperse dyestuff |
| CN103613511A (en) * | 2013-12-11 | 2014-03-05 | 江苏吉华化工有限公司 | Dilute sulfuric acid diazotization process of substituted phenylamine |
| CN104744217A (en) * | 2013-12-27 | 2015-07-01 | 江苏扬农化工集团有限公司 | Hydroquinone synthesis method |
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2015
- 2015-12-01 CN CN201510866795.9A patent/CN105418453A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232409A (en) * | 2012-12-31 | 2013-08-07 | 上海安诺其纺织化工股份有限公司 | Preparation method of disperse dyestuff |
| CN103613511A (en) * | 2013-12-11 | 2014-03-05 | 江苏吉华化工有限公司 | Dilute sulfuric acid diazotization process of substituted phenylamine |
| CN104744217A (en) * | 2013-12-27 | 2015-07-01 | 江苏扬农化工集团有限公司 | Hydroquinone synthesis method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187814A (en) * | 2016-06-29 | 2016-12-07 | 浙江闰土研究院有限公司 | A kind of synthetic method of disperse dyes diazol |
| CN108929244A (en) * | 2018-08-07 | 2018-12-04 | 江苏之江化工有限公司 | A kind of diazonium method of tide product nitrobenzene amine |
| CN111018806A (en) * | 2019-12-25 | 2020-04-17 | 安道麦安邦(江苏)有限公司 | Method and device for continuously preparing 5-amino-1, 2, 3-thiadiazole |
| CN111018806B (en) * | 2019-12-25 | 2024-04-12 | 安道麦安邦(江苏)有限公司 | Method and device for continuously preparing 5-amino-1, 2, 3-thiadiazole |
| CN115353751A (en) * | 2022-08-26 | 2022-11-18 | 浙江闰土染料有限公司 | Preparation method of monoazo disperse dye |
| CN115353751B (en) * | 2022-08-26 | 2023-11-14 | 浙江闰土染料有限公司 | Method for preparing monoazo disperse dye |
| CN116814089A (en) * | 2023-02-01 | 2023-09-29 | 山东安诺其精细化工有限公司 | Process for synthesizing disperse dye and disperse dye |
| CN116814089B (en) * | 2023-02-01 | 2024-06-21 | 山东安诺其精细化工有限公司 | Process for synthesizing disperse dye and disperse dye |
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Application publication date: 20160323 |