CN103030996A - Reactive red dye and its preparation method - Google Patents
Reactive red dye and its preparation method Download PDFInfo
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- CN103030996A CN103030996A CN2010102660370A CN201010266037A CN103030996A CN 103030996 A CN103030996 A CN 103030996A CN 2010102660370 A CN2010102660370 A CN 2010102660370A CN 201010266037 A CN201010266037 A CN 201010266037A CN 103030996 A CN103030996 A CN 103030996A
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Abstract
The invention relates to a reactive red dye and its preparation method. The dye is a compound having a structure represented by formula (I). The preparation method of the dye comprises the following steps: 1, adding an ethanolamine sulfate solution to a cyanuric chloride solution for reacting to obtain a first condensation solution, and adding a J acid to the first condensation solution to obtain a second condensation solution; 2, adding a hydrochloric acid solution and a sodium nitrite solution to 4-aminodiphenylamine-2-sulfonic acid, reacting under a condition that the pH value is less than 2, and eliminating excess nitrous acid by sulfamic acid to obtain a diazo solution; 3, adding the diazo solution obtained in step 2 to the second condensation solution obtained in step 1 in a dropwise manner to obtain a coupling reaction solution; 4, heating the coupling reaction solution obtained in step 3, maintaining the pH value in a range of 8-11, and hydrolyzing; 5, filtering the hydrolysis reaction solution obtained in step 4 to remove waste residues, and collecting the obtained filtrate; 6, carrying out colored light and intensity adjustment of the filtrate obtained in step 5; and 7, carrying out spray drying of the color solution obtained in step 6 to obtain the dye of the formula (I).
Description
Technical field
The present invention relates to a kind of nylon active dye well preparation method.Especially nylon red reactive dyes and preparation method thereof.
Background technology
Now the general nylon used dyestuff that dyes is matching stain, weak acid dye and metallized dye.Because the every wet fastness of nylon that these dyestuffs dye is not good enough, coloured light is not very gorgeous, and the low rate of clean absorption rate, the dyeing liquid waste concentration is high, and particularly heavy metal causes severe contamination to environment.Enter 21 century, because the restriction of environmental ecology, for dye uptake, the requirement of degree of fixation and dyeing waste liquid is more and more higher.Matching stain, weak acid dye and metal complex can not satisfy the dyeing nylon demand.
Be badly in need of at present environmental contamination reduction and raw materials cost low, beautiful in colour, the excellent nylon reactive red dye of every wet fastness properties.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of red nylon active dye well its preparation method, this dyestuff is as shown in the formula the compound shown in (I):
Wherein: M is-H or basic metal that preferred as alkali is Na or K.
The preparation method of the dye composition of above-mentioned formula (I) comprises the steps:
A, condensation reaction:
Thanomin sulfuric ester solution joins reaction acquisition primary condensation liquid in the cyanuric chloride solution, then adds J acid in this condensated liquid, obtains the secondary condensated liquid;
B, diazotization reaction:
In 4-ADPA-2-sulfonic acid, add hydrochloric acid soln and sodium nitrite solution, in the situation that react PH＜2, then eliminate excessive nitrite with thionamic acid, get diazo liquid;
C, coupled reaction:
B step gained diazo liquid is added drop-wise in the secondary condensated liquid of a step, gets coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is heated up, keep the pH=8-11 hydrolysis;
E, removal insolubles:
D step hydrolysis reaction liquid is filtered the removal waste residue, collect filtrate;
F, adjustment coloured light and intensity:
E step filtrate is carried out coloured light, intensity adjustment;
G, drying:
The look liquid of f step is carried out spraying drying, get formula (I) the finished product.
Preferably, the preparation method of the dye composition of above-mentioned formula (I) comprises the steps:
A, condensation reaction:
The thanomin sulfuric ester solution of pH=2-5 is joined in the cyanuric chloride solution, keep T=0-15 ℃, pH=2-3.5 reacted 4-6 hour, obtain primary condensation liquid, then in this condensated liquid, add J acid, adjust T=15-40 ℃, pH=4-6 reacted 2-4 hour, obtained the secondary condensated liquid;
B, diazotization reaction:
Add hydrochloric acid soln and sodium nitrite solution in low temperature 4-ADPA-2-sulfonic acid, at T=0-20 ℃, reacted 1-3 hour PH＜2, eliminates excessive nitrite with thionamic acid, gets diazo liquid;
C, coupled reaction:
B step gained diazo liquid is added drop-wise in the secondary condensated liquid of a step, keeps T=10-20 ℃, pH=5-7 reacted 1-2 hour, got coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is warming up to 30-50 ℃, keeps pH=8-11, reacted 5-7 hour;
E, removal insolubles:
D step hydrolysis reaction liquid is joined in the solid-liquid separator, separate, remove waste residue, collect filtrate in storage tank;
F, adjustment coloured light and intensity:
With the dyeing of e step filtrate, carry out coloured light, intensity adjustment according to coloration result again;
G, drying:
The look liquid of f step is joined in the feed liquid preheater, adjust inlet temperature and temperature out and carry out spraying drying, get formula (I) the finished product.
Preferably, the preparation method of the dye composition of above-mentioned formula (I) comprises the steps:
A, condensation reaction:
In dissolving vessel, add water of a small amount of end and thanomin sulfuric ester, use NaHCO
3Be neutralized to pH=2-5, get thanomin sulfuric ester solution; In reactor, add a small amount of water and a small amount of trash ice, add again cyanuric chloride, in the stirring, drip thanomin sulfuric ester solution, T=0-15 ℃, pH=2-3.5 dropwises, and reacts 4-6 hour, obtain primary condensation liquid, then in this condensated liquid, add J acid, adjust T=15-40 ℃, pH=4-6, reacted 2-4 hour, and obtained the secondary condensated liquid;
B, diazotization reaction:
Add end water and 4-ADPA-2-sulfonic acid in reactor, stir, add hydrochloric acid soln and the sodium nitrite solution of trash ice and 30%, at T=0-20 ℃, reacted 1-3 hour PH＜2, eliminates excessive nitrite with thionamic acid, gets diazo liquid;
C, coupled reaction:
B step gained diazo liquid is added drop-wise in the secondary condensated liquid of a step, in the dropping process T=10-20 ℃, transfer pH=5-7 with soda ash, drip and finish, reacted 1-2 hour, get coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is warming up to 30-50 ℃, keeps pH=8-11 with soda ash, reacted 5-7 hour;
E, removal insolubles:
D step hydrolysis reaction liquid is joined in the solid-liquid separator, separate, remove waste residue, collect filtrate in storage tank;
F, adjustment coloured light and intensity:
With the dyeing of e step filtrate, carry out coloured light, intensity adjustment according to coloration result again;
G, drying:
The look liquid of f step is joined in the feed liquid preheater, adjust 210 ℃ of inlet temperatures, carry out spraying drying with 95-100 ℃ temperature out, get formula (I) the finished product.
In the aforesaid method, preferably, in the primary condensation liquid preparation T=5-10 ℃, the reaction times is 5 hours;
In the aforesaid method, preferably, in the secondary condensated liquid preparation T=20-30 ℃, the reaction times is 3 hours;
In the aforesaid method, preferably, in the diazotization reaction T=5-15 ℃, the reaction times is 2 hours;
Wherein the structure of thanomin sulfuric ester is as follows:
H
2NCH
2CH
2OSO
3H
The structure of cyanuric chloride is as follows:
The structure of J acid is as follows:
The structure of 4-ADPA-2-sulfonic acid is as follows:
Used intermediate all is disclosed known compound in the prior art in the aforesaid method, and all the energy gum is bought from the market and obtained.
In the aforesaid method, what T represented is temperature, and for example T=10-20 ℃, the expression temperature is between 10-20 ℃.
The present invention also provides a kind of composition for dyeing nylon, and said composition comprises dye composition and the dyestuff carrier of formula (I).
The present invention also provides the dye composition of above-mentioned formula (I) to be used for the purposes of dyeing nylon.
The preparation of the dyestuff of above-mentioned formula (I) compound and use can environmental contamination reduction particularly reduces the pollution of heavy metal.And the desired raw material cost is low, and is beautiful in colour, every wet fastness, such as wet rub, soap, the excellent performances such as alkali sweat, sour sweat, washing, easy to use, be the excellent nylon reactive red dye that is applicable to dyeing nylon.
Embodiment
The preparation of the nylon reactive red dye compound of embodiment 1 structural formula (II)
The preparation of a, condenses:
In dissolving vessel, add water of a small amount of end and thanomin sulfuric ester 27Kg, use NaHCO
3In and pH=4-5, get thanomin sulfuric ester solution; In reactor, add a small amount of water and a small amount of trash ice, add again cyanuric chloride 19Kg, in the stirring, drip the thanomin sulfuric ester, T=0-15 ℃, pH=2-3.5 dropwises, and reacts 5 hours, gets primary condensation liquid; Add J acid 26.5Kg in primary condensation liquid, adjust T=35-40 ℃, pH=5-6 reacted 3 hours, got the secondary condensated liquid.
B, 4-ADPA-2-sulfonic acid diazotization:
In reactor, add end water, 4-ADPA-2-sulfonic acid 23.2Kg, stir, add trash ice, 30% hydrochloric acid soln and sodium nitrite solution.At 15-20 ℃, reacted 2 hours PH＜2, and (starch potassium iodide paper is little blueness after soaking), eliminate excessive nitrite with thionamic acid, get diazo liquid.
C, coupled reaction:
The diazo liquid that the b step is obtained is added drop-wise in a step secondary condensated liquid, drips T=15-20 ℃ of process, transfers pH=5-7 with soda ash, drips and finishes, and reacts 2 hours, gets coupled reaction liquid.
D, hydrolysis reaction:
C step coupled reaction liquid is warming up to 45-50 ℃, keeps pH=10-11 with soda ash, reacted 6 hours.
E, removal insolubles:
D step hydrolysis reaction liquid is joined in the solid-liquid separator, separate, remove waste residue, collect filtrate in storage tank.
F, adjustment coloured light and intensity:
With the dyeing of e step material, carry out coloured light, intensity adjustment according to coloration result again
G, drying:
The look liquid of f step is joined in the feed liquid preheater, adjust 210 ℃ of inlet temperatures, carry out spraying drying with 95-100 ℃ temperature out, get the finished product 101Kg.
The application performance table of the nylon reactive red dye of the formula of embodiment 1 (II)
The preparation method of dyestuff of the present invention and dyestuff thereof is described by specific embodiment.Those skilled in the art can use for reference the links such as content appropriate change raw material of the present invention, processing condition and realize corresponding other purpose, its relevant change does not all break away from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and all be deemed to be included within the scope of the present invention.
Claims (7)
1. red nylon active dyestuff, this dyestuff is as shown in the formula the compound shown in (I):
Wherein: M is-H or basic metal that preferred as alkali is Na or K.
2. the preparation method of dyestuff claimed in claim 1, the method comprises the steps:
A, condensation reaction:
Thanomin sulfuric ester solution joins reaction acquisition primary condensation liquid in the cyanuric chloride solution, then adds J acid in this condensated liquid, obtains the secondary condensated liquid;
B, diazotization reaction:
In 4-ADPA-2-sulfonic acid, add hydrochloric acid soln and sodium nitrite solution, in the situation that react PH＜2, then eliminate excessive nitrite with thionamic acid, get diazo liquid;
C, coupled reaction:
B step gained diazo liquid is added drop-wise in the secondary condensated liquid of a step, gets coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is heated up, keep the pH=8-11 hydrolysis;
E, removal insolubles:
D step hydrolysis reaction liquid is filtered the removal waste residue, collect filtrate;
F, adjustment coloured light and intensity:
E step filtrate is carried out coloured light, intensity adjustment;
G, drying:
The look liquid of f step is carried out spraying drying, get formula (I) the finished product.
3. method according to claim 2, the method comprises the steps:
A, condensation reaction:
The thanomin sulfuric ester solution of pH=2-5 is joined in the cyanuric chloride solution, keep T=0-15 ℃, pH=2-3.5 reacted 4-6 hour, obtain primary condensation liquid, then in this condensated liquid, add J acid, adjust T=15-40 ℃, pH=4-6 reacted 2-4 hour, obtained the secondary condensated liquid;
B, diazotization reaction:
Add hydrochloric acid soln and sodium nitrite solution in low temperature 4-ADPA-2-sulfonic acid, at T=0-20 ℃, reacted 1-3 hour PH＜2, eliminates excessive nitrite with thionamic acid, gets diazo liquid;
C, coupled reaction:
B step gained diazo liquid is added drop-wise in the secondary condensated liquid of a step, keeps T=10-20 ℃, pH=5-7 reacted 1-2 hour, got coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is warming up to 30-50 ℃, keeps pH=8-11, reacted 5-7 hour;
E, removal insolubles:
D step hydrolysis reaction liquid is joined in the solid-liquid separator, separate, remove waste residue, collect filtrate in storage tank;
F, adjustment coloured light and intensity:
With the dyeing of e step filtrate, carry out coloured light, intensity adjustment according to coloration result again;
G, drying:
The look liquid of f step is joined in the feed liquid preheater, adjust inlet temperature and temperature out and carry out spraying drying, get formula (I) the finished product.
4. described method according to claim 2-3, the method comprises the steps:
A, condensation reaction:
In dissolving vessel, add water of a small amount of end and thanomin sulfuric ester, use NaHCO
3Be neutralized to pH=2-5, get thanomin sulfuric ester solution; In reactor, add a small amount of water and a small amount of trash ice, add again cyanuric chloride, in the stirring, drip thanomin sulfuric ester solution, T=0-15 ℃, pH=2-3.5 dropwises, and reacts 4-6 hour, obtain primary condensation liquid, then in this condensated liquid, add J acid, adjust T=15-40 ℃, pH=4-6, reacted 2-4 hour, and obtained the secondary condensated liquid;
B, diazotization reaction:
Add end water and 4-ADPA-2-sulfonic acid in reactor, stir, add hydrochloric acid soln and the sodium nitrite solution of trash ice and 30%, at T=0-20 ℃, reacted 1-3 hour PH＜2, eliminates excessive nitrite with thionamic acid, gets diazo liquid;
C, coupled reaction:
B step gained diazo liquid is added drop-wise in the secondary condensated liquid of a step, in the dropping process T=10-20 ℃, transfer pH=5-7 with soda ash, drip and finish, reacted 1-2 hour, get coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is warming up to 30-50 ℃, keeps pH=8-11 with soda ash, reacted 5-7 hour;
E, removal insolubles:
D step hydrolysis reaction liquid is joined in the solid-liquid separator, separate, remove waste residue, collect filtrate in storage tank;
F, adjustment coloured light and intensity:
With the dyeing of e step filtrate, carry out coloured light, intensity adjustment according to coloration result again;
G, drying:
The look liquid of f step is joined in the feed liquid preheater, adjust 210 ℃ of inlet temperatures, carry out spraying drying with 95-100 ℃ temperature out, get formula (I) the finished product.
5. method according to claim 4, wherein in the preparation of primary condensation liquid T=5-10 ℃, the reaction times is 5 hours.
6. method according to claim 4, wherein in the preparation of secondary condensated liquid T=20-30 ℃, the reaction times is 3 hours.
7. method according to claim 4, wherein in the diazotization reaction T=5-15 ℃, the reaction times is 2 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010266037.0A CN103030996B (en) | 2010-08-30 | 2010-08-30 | Reactive red dye and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010266037.0A CN103030996B (en) | 2010-08-30 | 2010-08-30 | Reactive red dye and its preparation method |
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| CN103030996A true CN103030996A (en) | 2013-04-10 |
| CN103030996B CN103030996B (en) | 2014-04-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243776A (en) * | 2016-07-26 | 2016-12-21 | 萧县凯奇化工科技有限公司 | A kind of Yellow active dye composition and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4474697A (en) * | 1977-06-29 | 1984-10-02 | Bayer Aktiengeselschaft | Fluorotriazine-group-containing azo dyestuffs |
| EP0131542A1 (en) * | 1983-06-10 | 1985-01-16 | Ciba-Geigy Ag | Reactive dyes, their preparation and their use |
| AU647238B2 (en) * | 1991-02-27 | 1994-03-17 | Sumitomo Chemical Company, Limited | Monoazo compounds and method for dyeing or printing fiber materials using the same |
| JP2540598B2 (en) * | 1988-06-07 | 1996-10-02 | 日本化薬株式会社 | Reactive dye and dyeing method using the same |
| JP2001348505A (en) * | 2000-06-08 | 2001-12-18 | Sumitomo Chem Co Ltd | Reactive dye composition and application of the same to fiber |
| US20100132135A1 (en) * | 2005-07-08 | 2010-06-03 | Huntsman International Llc | Reactive dyes, a process for their preparation and their use |
-
2010
- 2010-08-30 CN CN201010266037.0A patent/CN103030996B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4474697A (en) * | 1977-06-29 | 1984-10-02 | Bayer Aktiengeselschaft | Fluorotriazine-group-containing azo dyestuffs |
| EP0131542A1 (en) * | 1983-06-10 | 1985-01-16 | Ciba-Geigy Ag | Reactive dyes, their preparation and their use |
| JP2540598B2 (en) * | 1988-06-07 | 1996-10-02 | 日本化薬株式会社 | Reactive dye and dyeing method using the same |
| AU647238B2 (en) * | 1991-02-27 | 1994-03-17 | Sumitomo Chemical Company, Limited | Monoazo compounds and method for dyeing or printing fiber materials using the same |
| JP2001348505A (en) * | 2000-06-08 | 2001-12-18 | Sumitomo Chem Co Ltd | Reactive dye composition and application of the same to fiber |
| US20100132135A1 (en) * | 2005-07-08 | 2010-06-03 | Huntsman International Llc | Reactive dyes, a process for their preparation and their use |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243776A (en) * | 2016-07-26 | 2016-12-21 | 萧县凯奇化工科技有限公司 | A kind of Yellow active dye composition and preparation method thereof |
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Address after: 300270 No. 1558 Kaixuan street, Dagang Petrochemical Industrial Park, Binhai New Area, Tianjin Patentee after: Tianjin Dek Chemical Co.,Ltd. Address before: 300163 Tianjin city Dongli District ZhangGuiZhuang road Ji'an Road Patentee before: Tianjin Dek Chemical Co.,Ltd. |
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