CN101353484B - Direct blended carbuncle D-BLL dye preparation technique - Google Patents
Direct blended carbuncle D-BLL dye preparation technique Download PDFInfo
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Abstract
The invention relates to a preparation process of a directly blended carbuncle D-BLL dye, comprising the steps of diazotization reaction, coupling reaction, a first condensation reaction, a second condensation reaction, a third condensation reaction, copper complex reaction and post treatment. The reaction conditions of the coupling reaction, the first condensation reaction and the second condensation reaction are optimized, thus saving the purification procedure and achieving the aim of improving production efficiency, saving energy and reducing exhaust.
Description
Technical field
The present invention relates to a kind of preparation technology's of direct blend dye, particularly a kind of direct blended carbuncle D-BLL preparation technology.
Background technology
Directly blended carbuncle D-BLL dye is to support to wash/cotton, the new dye of washing/glue mixed fibre " goes on foot single bath process " dyeing, by the washing of its support/cotton, wash/glue mixed fibre " goes on foot single bath process " dyeing, can significantly reduce the dyeing waste water quantity discharged, energy efficient, save man-hour, have advantages such as technology is easy, safe, economical, actual effect.In addition, it still is one of direct blend dye three-primary colours, not only can solid shade dyeing but also can piece together the union dyeing look with other direct blend dyes, and wide application, usage quantity is big.
Directly the structural formula of blended carbuncle D-BLL dye is as follows:
In the prior art, directly the preparation technology of blended carbuncle D-BLL dye mainly comprises the steps:
(1), diazotization reaction: diazotization reaction takes place in 0～5 ℃ and generates diazonium salt under hydrochloric acid and Sodium Nitrite effect in 1-hydroxyl-2-amino-4-Phenylsulfonic acid;
(2), coupled reaction: coupled reaction takes place and generates Monoazo compound in alkaline medium in above-mentioned diazonium salt and 2-amino-5-naphthols-7-sulfonic acid, and wherein, 2-amino-5-naphthols-relative diazonium salt of 7-sulfonic acid is excessive slightly, and the chemical equation of this reaction is:
When following above-mentioned reaction, the side reaction that also can have following reaction equation:
(3), purification process for the first time: heated up, saltout, filtered by the solution that above-mentioned coupled reaction took place, the reservation filter cake is removed the 2-amino-5-naphthols-7-sulfonic acid of above-mentioned side reaction generation by this operation, reaches the purification purpose;
(4), condensation reaction for the first time: described filter cake water and soda ash solution dissolve, with cyanuric chloride frozen water suspension, in 0～5 ℃, constantly regulate pH to 3 with 10% liquid caustic soda water, make its condensation reaction be tending towards obtaining the primary condensation thing fully, have by product to generate simultaneously;
(5), condensation reaction for the second time, the primary condensation thing slowly is warming up to 40～45 ℃, and constantly regulates pH to 6.5 with 10% liquid caustic soda water, carry out the secondary condensation reaction and obtain the secondary condenses, simultaneously, the by product generation is arranged;
(6), purify for the second time: saltout, filter, the by product of impurity and accumulation in step (4) and (5) is removed, keep filter cake, be the secondary condenses;
(7), condensation reaction for the third time: get filter cake water and soda ash dissolving by step (6), add thanomin, in 95 ℃, pH7～7.5 are carried out condensation reaction for the third time and are obtained condenses solution three times;
(8), copper complexing: after in three condenses solution that step (7) obtains, adding copper sulfate and thanomin, obtain copper network product solution until terminal point in 95～102 ℃ of back flow reaction;
(9), above-mentioned copper network product solution, by saltout, filter, dry described direct blended carbuncle D-BLL dye.
Above-mentioned technology is the more sophisticated operational path for preparing direct blended carbuncle D-BLL dye at present, can access the dye product that conforms to quality requirements basically.But the multistep purification step that comprises in this technology not only extends the production cycle, reduces production efficiency, and can produce a large amount of dyeing waste waters, is unfavorable for environment protection and save energy.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation technology that can save the direct blended carbuncle D-BLL dye of the intermediate purification step in the existing technology, rises this thereby enhance productivity, reduce discharge of wastewater and reduce to produce.
For solving above technical problem, the technical solution used in the present invention is:
A kind of preparation technology of direct blended carbuncle D-BLL dye, it is made up of following steps:
(1), diazotization reaction: 1-hydroxyl-2-amino-4-Phenylsulfonic acid generation diazotization reaction generates diazonium salt;
(2), coupled reaction: by the diazonium salt and the 2-amino-5-naphthols-7-sulfonic acid of step (1) gained, coupled reaction takes place under alkaline condition, obtain Monoazo compound solution, wherein the mol ratio of 2-amino-5-naphthols-7-sulfonic acid and 1-hydroxyl-2-amino-4-Phenylsulfonic acid is 1.0～0.99:1;
(3), condensation reaction for the first time: by step (2) gained Monoazo compound solution with after the cyanuric chloride suspensoid mixes, at 0～5 ℃, pH3～3.5 time reaction obtains primary condensation thing solution to terminal, and the mol ratio of wherein said cyanuric chloride and described 1-hydroxyl-2-amino-4-Phenylsulfonic acid is 1.0～0.99:1;
(4), condensation reaction for the second time: the primary condensation thing solution with step (3) gained, be warming up to 40～45 ℃, regulate pH6.7～6.8 with the mixing solutions of sodium-acetate and soda ash, carry out the condensation reaction second time, obtain secondary condenses solution to reaction end;
(5), condensation reaction for the third time: add thanomin in the secondary condenses solution of step (4) gained, at 90～95 ℃, pH7.0～7.5 back flow reaction get three condenses solution to reaction end;
(6), copper complex reaction: add copper sulfate in three condenses solution of step (5) gained, in 95～102 ℃, pH7.8～8.1 back flow reaction to reaction end obtains copper network product solution;
(7), aftertreatment: step (6) gained copper network product solution by saltouing, filtering, obtains described direct blended carbuncle D-BLL dye.
As further embodiment of the present invention: in the step (2), 2-amino-5-naphthols-7-sulfonic acid is dissolved in the grey black clear solution that obtains pH7.8～9 in the soda ash solution, add diazonium salt then at a slow speed by (1) gained, be incubated 12～15 ℃, constantly add soda ash to keep pH value of solution 7.8～9, until reaching reaction end.
Preferably, in the step (3), also adopt the mixing solutions of sodium-acetate and soda ash to come the pH of regulation system.
Above-mentioned " at a slow speed " is opposed with the feed way of " disposable adding ", and Jia Liao purpose is too fast for preventing feed rate at a slow speed, causes local acid-reaction, thereby may cause production of by-products.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
The present invention is on the basis of the traditional technology of the direct blended carbuncle D-BLL dye of preparation, condition to each step reaction is optimized, particularly the mole proportioning between the reaction raw materials is improved, and avoids production of by-products, thereby can save the secondary purification process of original technology intermediate steps.According to predesigne, owing to reduced the secondary purification process, compared with prior art, can reduce discharging waste water 50%, energy-conservation 20%, organic total amount reduces about 50% in the waste discharge; Simultaneously, owing to shortening the production cycle, improving reaction yield, the relative traditional technology of production efficiency of the present invention improves 20%.
Embodiment
Below the specific embodiment of the present invention is described:
Preparation technology according to direct blended carbuncle D-BLL dye of the present invention is made up of following steps:
(1), diazotization reaction:
With 0.2mol1-hydroxyl-2-amino-4-Phenylsulfonic acid and water, 0.5mol mixed in hydrochloric acid, at 10～15 ℃, add the 0.2mol30% sodium nitrite in aqueous solution in 45 minutes, react 1.5 hours must diazonium salt.
(2), coupled reaction:
At first, 0.2mol2-amino-5-naphthols-7-sulfonic acid and water is mixed, regulate pH8 with soda ash, make its dissolving be the grey black clear solution; Then, step (1) gained diazonium salt is slowly added in the grey black clear solution, 12～15 ℃ of temperature are constantly regulated with soda ash water, keep pH8～9, react 5 hours to terminal point, obtain monoazo product solution.
(3), condensation reaction for the first time:
The 0.1mol cyanuric chloride is mixed with less water and ice, stirred 30 minutes, be the fine suspension body.Above-mentioned monoazo product solution is slowly joined in the cyanuric chloride suspensoid, add in about 60 minutes, and constantly regulate pH, control pH3～3.5,0～5 ℃ of temperature with 10% sodium-acetate and 15% soda ash water; Reacted 3 hours, reaction is reached home, and gets primary condensation thing solution.
(4), condensation reaction for the second time
Step (3) gained primary condensation thing solution is slowly heated, and constantly regulate pH with 10% sodium-acetate and 15% soda ash water, temperature rises to 40～45 ℃ in about 2 hours, pH6.7～6.8; Reacted 3～4 hours, and got secondary condenses solution.
(5) condensation reaction for the third time
In gained secondary condenses solution, add the 0.73mol thanomin, regulate pH7.5,, reacted 3 hours, get three condenses solution at 90～95 ℃.
(6), copper complex reaction:
Add 0.18mol copper sulfate in three condenses solution of step (5) gained, adjust pH7.8～8.1, at 95～102 ℃, back flow reaction 3 hours gets copper complexing product solution.
(7), aftertreatment
Copper complexing product solution is cooled to 80 ℃, regulates pH5, saltout, stirred 30 minutes, filter with hydrochloric acid.Get 100% intensity finished product, 296 grams after filter cake oven dry, the markization, be direct blended carbuncle D-BLL dye, quality conformance with standard product.
The 1-hydroxyl of equal in quality-2-amino-4-Phenylsulfonic acid raw material can make direct blended carbuncle D-BLL dye finished product 235 grams at last by traditional technology, and yield is than method of the present invention low about 20%.
Owing to save the secondary filtration operation, the relative traditional technology of the technology of predesigne present embodiment can reduce discharging that total amount of organic reduces about 50% in the waste water of waste water 50%, energy-conservation 20%, discharging.
Claims (2)
1. the preparation technology of a direct blended carbuncle D-BLL dye, it is characterized in that: this preparation technology is made up of following steps:
(1), diazotization reaction: 1-hydroxyl-2-amino-4-Phenylsulfonic acid generation diazotization reaction generates diazonium salt;
(2), coupled reaction: by the diazonium salt and the 2-amino-5-naphthols-7-sulfonic acid of step (1) gained, coupled reaction takes place under alkaline condition, obtain Monoazo compound solution, wherein the mol ratio of 2-amino-5-naphthols-7-sulfonic acid and 1-hydroxyl-2-amino-4-Phenylsulfonic acid is 1.0～0.99: 1, specific operation process is as follows: 2-amino-5-naphthols-7-sulfonic acid is dissolved in the grey black clear solution that obtains pH 7.8～9 in the soda ash solution, add diazonium salt then at a slow speed by (1) gained, be incubated 12～15 ℃, constantly add soda ash to keep pH value of solution 7.8～9, until reaching reaction end;
(3), condensation reaction for the first time: by step (2) gained Monoazo compound solution with after the cyanuric chloride suspensoid mixes, at 0～5 ℃, 3～3.5 times reactions of pH obtain primary condensation thing solution to terminal, and the mol ratio of wherein said cyanuric chloride and described 1-hydroxyl-2-amino-4-Phenylsulfonic acid is 1.0～0.99: 1;
(4), condensation reaction for the second time: the primary condensation thing solution with step (3) gained, be warming up to 40～45 ℃, regulate pH 6.7～6.8 with the mixing solutions of sodium-acetate and soda ash, carry out the condensation reaction second time, obtain secondary condenses solution to reaction end;
(5), condensation reaction for the third time: add thanomin in the secondary condenses solution of step (4) gained, at 90～95 ℃, pH 7.0～7.5 back flow reaction get three condenses solution to reaction end;
(6), copper complex reaction: add copper sulfate in three condenses solution of step (5) gained, in 95～102 ℃, pH 7.8～8.1 back flow reaction to reaction end obtains copper network product solution;
(7), aftertreatment: step (6) gained copper network product solution by saltouing, filtering, obtains described direct blended carbuncle D-BLL dye.
2. the preparation technology of a kind of direct blended carbuncle D-BLL dye according to claim 1 is characterized in that: in the step (3), adopt the mixing solutions of sodium-acetate and soda ash to come the pH of regulation system.
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| CN111909536B (en) * | 2020-09-01 | 2022-04-05 | 浙江闰土染料有限公司 | Black direct dye composition, black direct dye and preparation method and application thereof |
| CN113502067B (en) * | 2021-08-16 | 2023-05-16 | 浙江闰土染料有限公司 | Preparation method of direct blending dye |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2001449A1 (en) * | 1970-01-14 | 1971-07-22 | Basf Ag | Process for the preparation of copper-containing disazo dyes |
| US4085097A (en) * | 1972-12-22 | 1978-04-18 | Ciba-Geigy Ag | Process for the manufacture of chromium complexes from metallizable azo or azo methine dyes |
| CN1179186A (en) * | 1995-03-17 | 1998-04-15 | 希巴特殊化学控股公司 | Process for increasing sun protection factor of cellulosic fibre materials |
| CA2421112A1 (en) * | 2000-08-28 | 2002-03-07 | Amrit P. Bindra | Heat stable monoazo magenta pigment compositions |
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- 2008-08-29 CN CN2008101957842A patent/CN101353484B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2001449A1 (en) * | 1970-01-14 | 1971-07-22 | Basf Ag | Process for the preparation of copper-containing disazo dyes |
| US4085097A (en) * | 1972-12-22 | 1978-04-18 | Ciba-Geigy Ag | Process for the manufacture of chromium complexes from metallizable azo or azo methine dyes |
| CN1179186A (en) * | 1995-03-17 | 1998-04-15 | 希巴特殊化学控股公司 | Process for increasing sun protection factor of cellulosic fibre materials |
| CA2421112A1 (en) * | 2000-08-28 | 2002-03-07 | Amrit P. Bindra | Heat stable monoazo magenta pigment compositions |
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Assignee: LIWANG CHEMICAL (NANTONG) Co.,Ltd. Assignor: WUJIANG MEIYAN SANYOU DYESTUFF CHEMICAL Co.,Ltd. Contract record no.: 2012320000106 Denomination of invention: Direct blended carbuncle D-BLL dye preparation technique Granted publication date: 20111228 License type: Exclusive License Open date: 20090128 Record date: 20120227 |
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Address after: 215225 Wujiang City, Jiangsu Province Ping Wang Zhen Mei Yan Shuangqiao Village Patentee after: Suzhou Meiyan Sanyou dye chemical (Group) Co.,Ltd. Address before: 215225 Wujiang City, Jiangsu Province Ping Wang Zhen Mei Yan Shuangqiao Village Patentee before: WUJIANG MEIYAN SANYOU DYESTUFF CHEMICAL Co.,Ltd. |
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Effective date of registration: 20230420 Address after: 017000 Yellow River Road East, Jianshe Road West, municipal road south, Mengxi Town, Etuoke Banner, Ordos City, Inner Mongolia Autonomous Region Patentee after: INNER MONGOLIA MEILIJIAN TECHNOLOGY CHEMICAL CO.,LTD. Address before: 215225 Wujiang City, Jiangsu Province Ping Wang Zhen Mei Yan Shuangqiao Village Patentee before: Suzhou Meiyan Sanyou dye chemical (Group) Co.,Ltd. |
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