CN101805527A - Method for preparing 4-methyl nitrobenzene-2-sulfonic acid self-polycondensation dye liquid color paste - Google Patents
Method for preparing 4-methyl nitrobenzene-2-sulfonic acid self-polycondensation dye liquid color paste Download PDFInfo
- Publication number
- CN101805527A CN101805527A CN 201010145865 CN201010145865A CN101805527A CN 101805527 A CN101805527 A CN 101805527A CN 201010145865 CN201010145865 CN 201010145865 CN 201010145865 A CN201010145865 A CN 201010145865A CN 101805527 A CN101805527 A CN 101805527A
- Authority
- CN
- China
- Prior art keywords
- polycondensation
- alkali
- liquid
- sulfonic acid
- sodium hydroxide
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 4-methyl nitrobenzene-2-sulfonic acid self-polycondensation dye liquid color paste, comprising the following steps of: dissolving 4-methyl nitrobenzene-2-sulfonic acid group methylbenzene into mixed solution of triethanolamine and diethylene glycol monomethylet, dropwise adding sodium hydroxide water solution into the mixed solution with high concentration to react and obtain an alkali coarse toning phase polycondensation reaction liquid; dropwise adding sodium hydroxide water solution into the mixed solution with low concentration to the alkali crude toning phase polycondensation reaction liquid to obtain an alkali fine toning phase polycondensation reaction liquid; adding water into the alkali fine toning phase polycondensation reaction liquid to react and obtain an alkalinity-reducing polycondensation reaction liquid; and adding ethylene glycol methyl ether into the alkalinity-reducing polycondensation reaction liquid for diluting, regulating pH by using NaHSO4 and regulating pH by using tetramethylammonium hydroxide water solution, recycling ethylene glycol methyl ether through condensing a filtering liquid after filtering to obtain the 4-methyl nitrobenzene-2-sulfonic acid self-polycondensation dye liquid color paste. The invention has the advantages of less three-waste generation, low production cost, simple process and easy control.
Description
Technical field
The present invention relates to a kind of preparation method of 4-p-nitrotoluene-o-sulfonic acid 4-self-polycondensation dye liquid color paste, belong to the dyestuff chemistry technical field.
Background technology
4-p-nitrotoluene-o-sulfonic acid 4-self-polycondensation dye according to the polycondensation degree can be divided into color from Huang to red dyestuff, wherein most widely used direct yellow 11 dyestuffs are a kind of strong yellow dyess, are specially adapted to the dyeing of fiber, leather etc.Narrate as institutes such as United States Patent (USP)s 4310331, its production process mainly is: the 4-p-nitrotoluene-o-sulfonic acid 4-under the catalysis of alkali metal hydroxide especially sodium hydroxide in 50-90 ℃ of following self-condensation reaction half head to a few hours, with in sulfuric acid or the hydrochloric acid and excessive alkali, obtain directly yellow 11 wet cakes by filter press technique at last again.Product can directly go on the market with wet cake or dried powder-form, but owing to contain a large amount of sodium ions in this technology, forms a large amount of complex compounds, causes the solvability of this mill base in water very poor (1-5% is only arranged), application difficult.In addition, the production of dry powder and also exist environmental problem such as dust pollution when using.The liquid-type dyestuff can overcome these shortcomings, therefore is subjected to market especially and welcomes.
The difficult point of liquid-type DYE PRODUCTION is to improve the solvability of dyestuff and the stability in storage of solution, so its key is how to reduce the content of salt in the mill base solution.The most direct method is that the mill base dyestuff is adopted sulfuric acid or hcl acidifying, but has two problems: 1) acidization mill base foxy is bigger, and 2) alkalimetal ion such as Na
+Existence cause high viscosity mill base gel formation and be difficult to filtering.Adopting the ether derivant of many alkyl alcoholamines and ethylene glycol or many ethylene glycol in the United States Patent (USP) 4310331 is solvent, from polycondensation, can obtain concentrating directly yellow 11 mill base solution by catalysis such as sodium hydroxids.But this method form and aspect control is difficult, and the low-temperature stability of solution is relatively poor.United States Patent (USP) 3905949, German Patent 3046450 grades adopt lithium hydroxide to cooperate catalysis with amine, have problems such as low-temperature stability difference too.United States Patent (USP)s 4502864,4617380,4617381 etc. then adopt the wet cake of preparation mill base earlier, further adopt alkylamine, alkyl alcoholamine, crown ether, hexafluoro methyl siliconic acid etc. to handle wet cake again, thereby obtain stable mill base solution.The shortcoming of these methods be or technology complicated, perhaps relate to a large amount of expensive raw materials.Also have patent directly to adopt organic bases alternate base metal hydroxides catalysis 4-p-nitrotoluene-o-sulfonic acid 4-from polycondensation, though obtain form and aspect easily control and the good mill base solution of stabilizability so easily, because the organic bases consumption is very big, its production cost is higher.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of 4-p-nitrotoluene-o-sulfonic acid 4-self-polycondensation dye liquid color paste, this procedure is simple, and the color of dye liquid mill base is easily controlled, the standing storage stable performance under-10-40 ℃ condition of prepared dye paste.
The present invention is realized that by the following technical programs a kind of preparation method of 4-p-nitrotoluene-o-sulfonic acid 4-self-polycondensation dye liquid color paste is characterized in that comprising following process:
1. 1 mole of 4-nitro-2-sulfonic group toluene is dissolved in trolamine and diethylene glycol dimethyl ether is 1 by volume: in the mixing solutions of the 350-450mL of 1-1.5, stirring obtains from polycondensation stoste, be warming up to after 55 ℃ to wherein dripping the aqueous sodium hydroxide solution that mass concentration is the 0.6-1.2 mole of 30%-40% from polycondensation stoste, 50-60 ℃ of hierarchy of control temperature reacted and obtained alkali coarse adjustment form and aspect polycondensation liquid after 1-1.5 hour;
2. the alkali coarse adjustment form and aspect polycondensation drop that makes to step 1 adds the aqueous sodium hydroxide solution that mass concentration is the 0.1-0.6 mole of 10%-20%, and control pH value＞14 and temperature 50-60 ℃, continue to react after 0.5-1 hour obtaining alkali fine tuning form and aspect polycondensation liquid;
3. the alkali fine tuning form and aspect polycondensation liquid that makes to step 2 adds 70-100mL water, and control pH value be 12-14 and temperature 50-60 ℃, and continuation is reacted after 0.5-1 hour and being obtained falling alkali polycondensation liquid;
4. the alkali polycondensation liquid that falls that makes to step 3 subsequently adds ethylene glycol monomethyl ether and is diluted to apparent viscosity less than 2000 milli handkerchiefs during second, and uses solid NaHSO
4Regulating pH is 3～4, is 50% tetramethylammonium hydroxide aqueous solution adjusting pH to 7-7.5 then with mass concentration, and after filtering, filtrate concentrates and reclaim the solvent ethylene glycol methyl ether in the filtrate, obtains 4-p-nitrotoluene-o-sulfonic acid 4-self-polycondensation dye liquid color paste.
It is few to the invention has the advantages that its three wastes produce, and production cost is lower, and preparation process is simple, easy to operate.Make the product form and aspect be easy to control by add the sodium hydroxide mode in batches: to adopt high-concentration sodium hydroxide to be used for its whole form and aspect of coarse regulation for the first time, that adopts for the second time low-concentration sodium hydroxide is used for the whole form and aspect of fine adjustment, at last by adding the naoh concentration that water reduces whole system, thereby reach the product distribution of polymerization degree that narrows, inching body colour mutually to the purpose that requires.The 4-p-nitrotoluene-o-sulfonic acid 4-self-polycondensation dye liquid good stability of gained can be in standing storage under the-10-40 ℃ condition.
Embodiment
Embodiment 1:
Add 300g (＞80%) 4-nitro-2-sulfonic group toluene in there-necked flask, 250mL trolamine and 350mL diethylene glycol dimethyl ether start and stir and slowly intensification, and material dissolves gradually and is faint yellow transparent settled solution; When temperature reached 55 ℃, beginning to drip the 150mL mass concentration was 33% aqueous sodium hydroxide solution, and hierarchy of control temperature must not be above 60 ℃, and this moment, solution colour was deepened gradually by xanthochromia is red; Keep solution to stir 1 hour under 60 ℃ of temperature then, this moment, solution was the muddy liquid of shallow red sauce, i.e. alkali coarse adjustment form and aspect polycondensation liquid; Under 60 ℃ of conditions of control solution temperature, adding the 50mL mass concentration to system is 20% aqueous sodium hydroxide solution again, and control reaction 30 minutes obtains dark red sauce alkali fine tuning form and aspect polycondensation liquid; Add entry 100ml to system again, continue hierarchy of control stirring reaction 30min under 60 ℃ of temperature, obtain falling alkali polycondensation liquid; Add ethylene glycol monomethyl ether 300mL to system at last, and use solid NaHSO
4Regulating pH is 3～4, be that 50% tetramethylammonium hydroxide aqueous solution is regulated pH to 7-7.5 with mass concentration then, filter that filtrate concentrates and reclaim the solvent ethylene glycol methyl ether in the filtrate, can obtain a kind of yellow dyes (direct yellow 11# concentrated solution), λ max=380nm.
Embodiment 2:
Experimental procedure is with embodiment 1.Just be with the 150mL mass concentration 33% aqueous sodium hydroxide solution to change the 160mL mass concentration into be 35% aqueous sodium hydroxide solution, resulting dyestuff (concentrated solution) is an orange, λ max=382nm.
Embodiment 3:
Experimental procedure is with embodiment 1.Just the 50mL mass concentration be 20% aqueous sodium hydroxide solution to change the 40mL mass concentration into be 20% aqueous sodium hydroxide solution, resulting dyestuff (concentrated solution) is a yellow-green colour, λ max=377nm.
Embodiment 4:
Add 300g (＞80%) 4-nitro-2-sulfonic group toluene in there-necked flask, 250mL trolamine and 250mL diethylene glycol dimethyl ether start and stir and slowly intensification, and material dissolves gradually and is faint yellow transparent settled solution; When temperature reached 55 ℃, beginning to drip the 100mL mass concentration was 40% aqueous sodium hydroxide solution, and hierarchy of control temperature must not be above 60 ℃, and this moment, solution colour was deepened gradually by xanthochromia is red; Keep solution to stir 1.5 hours under 60 ℃ of temperature then, this moment, solution was the muddy liquid of shallow red sauce, i.e. alkali coarse adjustment form and aspect polycondensation liquid; Under 60 ℃ of conditions of control solution temperature, adding the 60mL mass concentration to system is 20% aqueous sodium hydroxide solution again, and control reaction 30 minutes obtains alkali fine tuning form and aspect polycondensation liquid; Add entry 120ml to system again, continue hierarchy of control stirring reaction 1min under 60 ℃ of temperature and obtain falling alkali polycondensation liquid; Add ethylene glycol monomethyl ether 250mL to system at last, and use solid NaHSO
4Regulating pH is 3～4, regulates pH to 7-7.5 with 50% tetramethylammonium hydroxide aqueous solution then, filters, and filtrate concentrates and reclaim the solvent ethylene glycol methyl ether in the filtrate, can obtain a kind of orange dyestuff (concentrated solution), λ max=385nm.
Embodiment 5:
Experimental procedure is with embodiment 4.Just be that to change the 80mL mass concentration into be 40% aqueous sodium hydroxide solution to 40% aqueous sodium hydroxide solution with the 100mL mass concentration, the 60mL mass concentration is that to change the 100mL mass concentration into be 10% aqueous sodium hydroxide solution to 20% aqueous sodium hydroxide solution, resulting dyestuff (concentrated solution) is a yellow-green colour, λ max=374nm.
Embodiment 6:
Experimental procedure is with embodiment 4.Just be that to change the 80mL mass concentration into be 40% aqueous sodium hydroxide solution to 40% aqueous sodium hydroxide solution with the 100mL mass concentration, the 60mL mass concentration is that mass concentration is that to change the 100mL mass concentration into be 20% aqueous sodium hydroxide solution to 20% aqueous sodium hydroxide solution, resulting dyestuff (concentrated solution) is a yellow-green colour, λ max=377nm.
Embodiment 7:
Add 300g (＞80%) 4-nitro-2-sulfonic group toluene in there-necked flask, 200mL trolamine and 300mL diethylene glycol dimethyl ether start and stir and slowly intensification, and material dissolves gradually and is faint yellow transparent settled solution; When temperature reached 55 ℃, beginning to drip the 190mL mass concentration was 30% aqueous sodium hydroxide solution, and hierarchy of control temperature must not be above 60 ℃, and this moment, solution colour was deepened gradually by xanthochromia is red; Keep solution to stir 1 hour under 60 ℃ of temperature then, this moment, solution was the muddy liquid of shallow red sauce, i.e. alkali coarse adjustment form and aspect polycondensation liquid; Under 60 ℃ of conditions of control solution temperature, adding the 70mL mass concentration to system is 20% aqueous sodium hydroxide solution again, and control reaction 1 hour obtains alkali fine tuning form and aspect polycondensation liquid; Add entry 120ml to system again, continue hierarchy of control stirring reaction 30min under 60 ℃ of temperature and obtain falling alkali polycondensation liquid; Add ethylene glycol monomethyl ether 300mL to system at last, and use solid NaHSO
4Regulating pH is 3～4, regulates pH to 7-7.5 with 50% tetramethylammonium hydroxide aqueous solution then, filters, and filtrate concentrates and reclaim the solvent ethylene glycol methyl ether in the filtrate, can obtain a kind of orange dyestuff (concentrated solution), λ max=391nm.
Embodiment 8:
Experimental procedure is with embodiment 7.Just be with the 70mL mass concentration 20% aqueous sodium hydroxide solution to change the 60mL mass concentration into be 20% aqueous sodium hydroxide solution, resulting dyestuff (concentrated solution) is an orange, λ max=384nm.
Embodiment 9:
Experimental procedure is with embodiment 7.Just be with the 70mL mass concentration 20% aqueous sodium hydroxide solution to change the 40mL mass concentration into be 20% aqueous sodium hydroxide solution, resulting dyestuff (concentrated solution) is a yellow-green colour, λ max=376nm.
Claims (1)
1. the preparation method of a 4-p-nitrotoluene-o-sulfonic acid 4-self-polycondensation dye liquid color paste is characterized in that comprising following process:
1) 1 mole of 4-nitro-2-sulfonic group toluene is dissolved in trolamine and diethylene glycol dimethyl ether is 1 by volume: in the mixing solutions of the 350-450mL of 1-1.5, stirring obtains from polycondensation stoste, be warming up to after 55 ℃ to wherein dripping the aqueous sodium hydroxide solution that mass concentration is the 0.6-1.2 mole of 30%-40% from polycondensation stoste, 50-60 ℃ of hierarchy of control temperature reacted and obtained alkali coarse adjustment form and aspect polycondensation liquid after 1-1.5 hour;
2) the alkali coarse adjustment form and aspect polycondensation drop that makes to step 1) adds the aqueous sodium hydroxide solution that mass concentration is the 0.1-0.6 mole of 10%-20%, and control pH value＞14 and temperature 50-60 ℃, continue to react after 0.5-1 hour obtaining alkali fine tuning form and aspect polycondensation liquid;
3) to step 2) the alkali fine tuning form and aspect polycondensation liquid that makes adds 70-100mL water, and control pH value be 12-14 and temperature 50-60 ℃, and continuation is reacted after 0.5-1 hour and being obtained falling alkali polycondensation liquid;
4) the alkali polycondensation liquid that falls that makes to step 3) subsequently adds ethylene glycol monomethyl ether and is diluted to apparent viscosity less than 2000 milli handkerchiefs during second, and uses solid NaHSO
4Regulating pH is 3～4, is 50% tetramethylammonium hydroxide aqueous solution adjusting pH to 7-7.5 then with mass concentration, and after filtering, filtrate concentrates and reclaim the solvent ethylene glycol methyl ether in the filtrate, obtains 4-p-nitrotoluene-o-sulfonic acid 4-self-polycondensation dye liquid color paste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010145865 CN101805527A (en) | 2010-04-14 | 2010-04-14 | Method for preparing 4-methyl nitrobenzene-2-sulfonic acid self-polycondensation dye liquid color paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010145865 CN101805527A (en) | 2010-04-14 | 2010-04-14 | Method for preparing 4-methyl nitrobenzene-2-sulfonic acid self-polycondensation dye liquid color paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101805527A true CN101805527A (en) | 2010-08-18 |
Family
ID=42607487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010145865 Pending CN101805527A (en) | 2010-04-14 | 2010-04-14 | Method for preparing 4-methyl nitrobenzene-2-sulfonic acid self-polycondensation dye liquid color paste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101805527A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312207A (en) * | 2014-09-12 | 2015-01-28 | 沈阳化工大学 | Method for improving direct yellow 11 dye-uptake |
| CN110373040A (en) * | 2019-07-30 | 2019-10-25 | 于克兢 | A kind of azoxy and azo stibene dyestuff preparation method |
| CN111905448A (en) * | 2020-07-09 | 2020-11-10 | 丁蒙双 | Pigment recovery device of printing equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4310331A (en) * | 1980-03-21 | 1982-01-12 | Produits Chimiques Ugine Kuhlmann | Process for the preparation of the dyestuff direct yellow 11 in the form of concentrated stable solutions, the solutions obtained and their applications |
| WO2001090257A2 (en) * | 2000-05-26 | 2001-11-29 | Ciba Specialty Chemicals Holding Inc. | Process for preparing solutions of anionic organic compounds |
| US20050132510A1 (en) * | 2003-12-22 | 2005-06-23 | Basf Akiengesellschaft | Liquid formulations of direct dyes |
-
2010
- 2010-04-14 CN CN 201010145865 patent/CN101805527A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4310331A (en) * | 1980-03-21 | 1982-01-12 | Produits Chimiques Ugine Kuhlmann | Process for the preparation of the dyestuff direct yellow 11 in the form of concentrated stable solutions, the solutions obtained and their applications |
| WO2001090257A2 (en) * | 2000-05-26 | 2001-11-29 | Ciba Specialty Chemicals Holding Inc. | Process for preparing solutions of anionic organic compounds |
| US20050132510A1 (en) * | 2003-12-22 | 2005-06-23 | Basf Akiengesellschaft | Liquid formulations of direct dyes |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312207A (en) * | 2014-09-12 | 2015-01-28 | 沈阳化工大学 | Method for improving direct yellow 11 dye-uptake |
| CN104312207B (en) * | 2014-09-12 | 2016-08-24 | 沈阳化工大学 | A kind of method improving the most yellow 11 dye-uptakes |
| CN110373040A (en) * | 2019-07-30 | 2019-10-25 | 于克兢 | A kind of azoxy and azo stibene dyestuff preparation method |
| CN110373040B (en) * | 2019-07-30 | 2021-05-14 | 洛阳美伦色彩科技有限公司 | Preparation method of azoxy and azostilbene dye |
| CN111905448A (en) * | 2020-07-09 | 2020-11-10 | 丁蒙双 | Pigment recovery device of printing equipment |
| CN111905448B (en) * | 2020-07-09 | 2022-01-28 | 浏阳市博德包装印刷有限公司 | Pigment recovery device of printing equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102757445B (en) | Preparation technique of isosorbide | |
| CN104693009B (en) | Naphthalene sulfonated products direct alkali fusion coproduction 1-naphthols and the method for beta naphthal | |
| CN101805527A (en) | Method for preparing 4-methyl nitrobenzene-2-sulfonic acid self-polycondensation dye liquid color paste | |
| CN101830546A (en) | Poly-aluminum chloride-magnesium printing and dyeing wastewater coagulant and preparation method thereof | |
| CN101962537A (en) | Method for preparing (Zn,Cd)S quantum dot | |
| CN106117042B (en) | The method that phenylacetic acid is recycled in the waste liquid of 6-amino-penicillanic acid is prepared from enzyme process | |
| CN102816166A (en) | Preparation method of zinc sodium chlorophyllate from silkworm excrement | |
| CN106192038B (en) | The preparation method of blue light luminous fiber | |
| CN107163051A (en) | A kind of preparation method of folic acid | |
| CN101054476A (en) | Method for preparing active blue dyestuff | |
| CN104447202B (en) | A kind of production method of potassium method tetramethylolmethane | |
| CN102127307A (en) | Recovered mixed alkali solution from production of indigo, and recovering method and use thereof | |
| CN102070523A (en) | Novel method for preparing 3-hydroxylquinaldine-4-carboxylic acid | |
| CN108409593A (en) | The synthesis technology of 2- amino -4- acetyl-anisidines | |
| CN103044949B (en) | Preparation method of yellow pigment | |
| CN104609757A (en) | Preparation and compound formulation method of cottonseed-dreg concrete foaming agent | |
| CN103396381B (en) | A kind of production method of hydrochlorothiazide | |
| CN103566952B (en) | CdS/Cd 2ge 2o 6the preparation method of composite photo-catalyst | |
| CN103304452B (en) | Method for extracting effective ingredients from aromatic sulfonic acid sodium derivative wastewater | |
| CN107324350A (en) | A kind of method for preparing nanoprecipitation silica using low-grade diatomite | |
| CN102786814A (en) | Preparation method for high energy saving environmental protection type phthalocyanine green pigment | |
| CN106365978A (en) | Preparation method for 2, 3-difluoro-6-methoxy benzoic acid | |
| CN103044948B (en) | Preparation method of red pigment | |
| CN104445128A (en) | Preparation method of battery-grade lithium dihydrogen phosphate | |
| CN103773079A (en) | Method for preparing pigment red 177 in ionic liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100818 |