CN103030996B - Reactive red dye and its preparation method - Google Patents
Reactive red dye and its preparation method Download PDFInfo
- Publication number
- CN103030996B CN103030996B CN201010266037.0A CN201010266037A CN103030996B CN 103030996 B CN103030996 B CN 103030996B CN 201010266037 A CN201010266037 A CN 201010266037A CN 103030996 B CN103030996 B CN 103030996B
- Authority
- CN
- China
- Prior art keywords
- liquid
- reaction
- solution
- hour
- 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.)
- Active
Links
Landscapes
- Coloring (AREA)
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). The formula (I) is shown in the description.
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 dyestuff used 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, dyeing liquid waste concentration is high, and particularly heavy metal, causes severe contamination to environment.Enter 21 century, due to 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 meet dyeing nylon demand.
Be badly in need of at present minimizing environmental pollution 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 the compound shown in following formula 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 in cyanuric chloride solution and obtains primary condensation liquid, then in this condensated liquid, adds J acid, obtains secondary condensated liquid;
B, diazotization reaction:
In 4-ADPA-2-sulfonic acid, add hydrochloric acid soln and sodium nitrite solution, the in the situation that of pH < 2, react, then with thionamic acid, eliminate excessive nitrite, obtain diazo liquid;
C, coupled reaction:
B step gained diazo liquid is added drop-wise in the secondary condensated liquid of a step, obtains coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is heated up, keep pH=8-11 hydrolysis;
E, removal insolubles:
D step hydrolysis reaction liquid is filtered and removes waste residue, collect filtrate;
F, adjustment coloured light and intensity:
E step filtrate is carried out to coloured light, intensity adjustment;
G, dry:
The look liquid of f step is sprayed dry, obtain 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 cyanuric chloride solution, keep T=0-15 ℃, pH=2-3.5, reaction 4-6 hour, obtain primary condensation liquid, then in this condensated liquid, add J acid, adjust T=15-40 ℃, pH=4-6, reaction 2-4 hour, obtains secondary condensated liquid;
B, diazotization reaction:
In low temperature 4-ADPA-2-sulfonic acid, add hydrochloric acid soln and sodium nitrite solution, at T=0-20 ℃, pH < 2, reaction 1-3 hour, eliminates excessive nitrite with thionamic acid, obtains 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, reaction 1-2 hour, obtains coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is warming up to 30-50 ℃, keeps pH=8-11, reaction 5-7 hour;
E, removal insolubles:
D step hydrolysis reaction liquid is joined in solid-liquid separator, carry out separation, remove waste residue, collect filtrate in storage tank;
F, adjustment coloured light and intensity:
With the dyeing of e step filtrate, then carry out coloured light, intensity adjustment according to coloration result;
G, dry:
The look liquid of f step is joined in feed liquid preheater, and adjustment inlet temperature and temperature out are sprayed dry, obtain 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, obtain thanomin sulfuric ester solution; In reactor, add a small amount of water and a small amount of trash ice, then add cyanuric chloride, in stirring, drip thanomin sulfuric ester solution, T=0-15 ℃, pH=2-3.5, dropwises, reaction 4-6 hour, obtain primary condensation liquid, then in this condensated liquid, add J acid, adjust T=15-40 ℃, pH=4-6, reaction 2-4 hour, obtains secondary condensated liquid;
B, diazotization reaction:
In reactor, add end water and 4-ADPA-2-sulfonic acid, stir, add hydrochloric acid soln and the sodium nitrite solution of trash ice and 30%, at T=0-20 ℃, pH < 2, reaction 1-3 hour, with thionamic acid, eliminate excessive nitrite, obtain diazo liquid;
C, coupled reaction:
B step gained diazo liquid is added drop-wise in the secondary condensated liquid of a step, and T=10-20 ℃ in dropping process, adjusts pH=5-7 with soda ash, drips and finishes, and reaction 1-2 hour, obtains coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is warming up to 30-50 ℃, with soda ash, keeps pH=8-11, reaction 5-7 hour;
E, removal insolubles:
D step hydrolysis reaction liquid is joined in solid-liquid separator, carry out separation, remove waste residue, collect filtrate in storage tank;
F, adjustment coloured light and intensity:
With the dyeing of e step filtrate, then carry out coloured light, intensity adjustment according to coloration result;
G, dry:
The look liquid of f step is joined in feed liquid preheater, adjust 210 ℃ of inlet temperatures, with the temperature out of 95-100 ℃, spray dry, obtain formula (I) the finished product.
In aforesaid method, preferably, T=5-10 ℃ in the preparation of primary condensation liquid, the reaction times is 5 hours;
In aforesaid method, preferably, T=20-30 ℃ in the preparation of secondary condensated liquid, the reaction times is 3 hours;
In aforesaid method, preferably, T=5-15 ℃ in diazotization reaction, 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:
In aforesaid method, intermediate used is all disclosed known compound in prior art, all can buy and obtain from the market.
In aforesaid method, what T represented is temperature, and for example T=10-20 ℃, represents that temperature is between 10-20 ℃.
The present invention also provides a kind of composition for the nylon that dyes, the dye composition that said composition comprises formula (I) and dyestuff carrier.
The present invention also provides the purposes of the dye composition of above-mentioned formula (I) for the nylon that dyes.
The preparation of the dyestuff of above-mentioned formula (I) compound and use can reduce environmental pollution, particularly reduce the pollution of heavy metal.And desired raw material cost is low, beautiful in colour, every wet fastness, such as wet rubbing, soap, the excellent performance 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, obtain thanomin sulfuric ester solution; In reactor, add a small amount of water and a small amount of trash ice, then add cyanuric chloride 19Kg, in stirring, drip thanomin sulfuric ester, T=0-15 ℃, pH=2-3.5, dropwises, and reacts 5 hours, obtains primary condensation liquid; In primary condensation liquid, add J acid 26.5Kg, adjust T=35-40 ℃, pH=5-6, reacts 3 hours, obtains 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 ℃, pH < 2, reacts 2 hours, and (starch potassium iodide paper is micro-blueness after soaking), with thionamic acid, eliminate excessive nitrite, obtain diazo liquid.
C, coupled reaction:
The diazo liquid that b step is obtained is added drop-wise in a step secondary condensated liquid, drips process T=15-20 ℃, with soda ash, adjusts pH=5-7, drips and finishes, and reacts 2 hours, obtains coupled reaction liquid.
D, hydrolysis reaction:
C step coupled reaction liquid is warming up to 45-50 ℃, with soda ash, keeps pH=10-11, react 6 hours.
E, removal insolubles:
D step hydrolysis reaction liquid is joined in solid-liquid separator, carry out separation, remove waste residue, collect filtrate in storage tank.
F, adjustment coloured light and intensity:
By the dyeing of e step material, then carry out coloured light, intensity adjustment according to coloration result
G, dry:
The look liquid of f step is joined in feed liquid preheater, adjust 210 ℃ of inlet temperatures, with the temperature out of 95-100 ℃, spray dry, obtain 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 object, its relevant change does not all depart from content of the present invention, within all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included in scope of the present invention.
Claims (8)
1. a red nylon active dyestuff, this dyestuff is the compound shown in following formula I:
Wherein: M is-H or basic metal.
2. red nylon active dyestuff according to claim 1, is characterized in that: described M is Na or K.
3. the preparation method of dyestuff claimed in claim 2, the method comprises the steps:
A, condensation reaction:
Thanomin sulfuric ester solution joins reaction in cyanuric chloride solution and obtains primary condensation liquid, then in this condensated liquid, adds J acid, obtains secondary condensated liquid;
B, diazotization reaction:
In 4-ADPA-2-sulfonic acid, add hydrochloric acid soln and sodium nitrite solution, the in the situation that of pH < 2, react, then with thionamic acid, eliminate excessive nitrite, obtain diazo liquid;
C, coupled reaction:
B step gained diazo liquid is added drop-wise in the secondary condensated liquid of a step, obtains coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is heated up, keep pH=8-11 hydrolysis;
E, removal insolubles:
D step hydrolysis reaction liquid is filtered and removes waste residue, collect filtrate;
F, adjustment coloured light and intensity:
E step filtrate is carried out to coloured light, intensity adjustment;
G, dry:
The look liquid of f step is sprayed dry, obtain formula (I) the finished product.
4. method according to claim 3, the method comprises the steps:
A, condensation reaction:
The thanomin sulfuric ester solution of pH=2-5 is joined in cyanuric chloride solution, keep T=0-15 ℃, pH=2-3.5, reaction 4-6 hour, obtain primary condensation liquid, then in this condensated liquid, add J acid, adjust T=15-40 ℃, pH=4-6, reaction 2-4 hour, obtains secondary condensated liquid;
B, diazotization reaction:
In low temperature 4-ADPA-2-sulfonic acid, add hydrochloric acid soln and sodium nitrite solution, at T=0-20 ℃, pH < 2, reaction 1-3 hour, eliminates excessive nitrite with thionamic acid, obtains 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, reaction 1-2 hour, obtains coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is warming up to 30-50 ℃, keeps pH=8-11, reaction 5-7 hour;
E, removal insolubles:
D step hydrolysis reaction liquid is joined in solid-liquid separator, carry out separation, remove waste residue, collect filtrate in storage tank;
F, adjustment coloured light and intensity:
With the dyeing of e step filtrate, then carry out coloured light, intensity adjustment according to coloration result;
G, dry:
The look liquid of f step is joined in feed liquid preheater, and adjustment inlet temperature and temperature out are sprayed dry, obtain formula (I) the finished product.
5. according to the method described in claim 3 or 4, 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, obtain thanomin sulfuric ester solution; In reactor, add a small amount of water and a small amount of trash ice, then add cyanuric chloride, in stirring, drip thanomin sulfuric ester solution, T=0-15 ℃, pH=2-3.5, dropwises, reaction 4-6 hour, obtain primary condensation liquid, then in this condensated liquid, add J acid, adjust T=15-40 ℃, pH=4-6, reaction 2-4 hour, obtains secondary condensated liquid;
B, diazotization reaction:
In reactor, add end water and 4-ADPA-2-sulfonic acid, stir, add hydrochloric acid soln and the sodium nitrite solution of trash ice and 30%, at T=0-20 ℃, pH < 2, reaction 1-3 hour, with thionamic acid, eliminate excessive nitrite, obtain diazo liquid;
C, coupled reaction:
B step gained diazo liquid is added drop-wise in the secondary condensated liquid of a step, and T=10-20 ℃ in dropping process, adjusts pH=5-7 with soda ash, drips and finishes, and reaction 1-2 hour, obtains coupled reaction liquid;
D, hydrolysis reaction:
C step coupled reaction liquid is warming up to 30-50 ℃, with soda ash, keeps pH=8-11, reaction 5-7 hour;
E, removal insolubles:
D step hydrolysis reaction liquid is joined in solid-liquid separator, carry out separation, remove waste residue, collect filtrate in storage tank;
F, adjustment coloured light and intensity:
With the dyeing of e step filtrate, then carry out coloured light, intensity adjustment according to coloration result;
G, dry:
The look liquid of f step is joined in feed liquid preheater, adjust 210 ℃ of inlet temperatures, with the temperature out of 95-100 ℃, spray dry, obtain formula (I) the finished product.
6. method according to claim 5, T=5-10 ℃ in the preparation of primary condensation liquid wherein, the reaction times is 5 hours.
7. method according to claim 5, T=20-30 ℃ in the preparation of secondary condensated liquid wherein, the reaction times is 3 hours.
8. method according to claim 5, T=5-15 ℃ in diazotization reaction wherein, the reaction times is 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010266037.0A CN103030996B (en) | 2010-08-30 | 2010-08-30 | Reactive red dye and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010266037.0A CN103030996B (en) | 2010-08-30 | 2010-08-30 | Reactive red dye and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103030996A CN103030996A (en) | 2013-04-10 |
| CN103030996B true CN103030996B (en) | 2014-04-30 |
Family
ID=48018418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010266037.0A Active CN103030996B (en) | 2010-08-30 | 2010-08-30 | Reactive red dye and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103030996B (en) |
Families Citing this family (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 (5)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY165913A (en) * | 2005-07-08 | 2018-05-18 | Ciba Specialty Chemicals Holding Inc | Reactive dyes, a process for their preparation and their use |
-
2010
- 2010-08-30 CN CN201010266037.0A patent/CN103030996B/en active Active
Patent Citations (5)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103030996A (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102040860B (en) | Dye suitable for nylon dyeing | |
| CN102040862A (en) | Nylon reactive red dye and preparation method thereof | |
| CN103030996B (en) | Reactive red dye and its preparation method | |
| CN103030999A (en) | Nylon reactive red dye and its preparation method | |
| CN103030997B (en) | Reactive red dye | |
| CN103031002B (en) | Nylon reactive red dye | |
| CN103044958B (en) | Nylon dye | |
| CN103044959B (en) | Reactive red dye suitable for nylon dyeing | |
| CN102040859B (en) | Dye and preparation method thereof | |
| CN102040863A (en) | Nylon dye and preparation method thereof | |
| CN102433024B (en) | A kind of red reactive dye for wool and preparation method thereof | |
| CN102040861A (en) | Reactive red dye suitable for dyeing nylon and preparation method thereof | |
| CN103030998B (en) | Nylon reactive red dye suitable for nylon dyeing, and its preparation method | |
| CN102321387B (en) | A kind of nylon reactive yellow dye and preparation method thereof | |
| CN101481522B (en) | Preparation of red reactive dye for fur | |
| CN103059600A (en) | Dye for dyeing nylon and preparation method thereof | |
| CN102391684A (en) | Yellow reactive dye for dyeing nylon and preparation method thereof | |
| CN102504581A (en) | Extra-dark black active dye and preparation method thereof | |
| CN102433025A (en) | Black active dye and preparation method thereof | |
| CN101735655B (en) | Red reactive dye for wool and preparation method thereof | |
| CN101705010B (en) | Purple reactive dye for wool | |
| CN102286217B (en) | Yellow active dye for hair and preparation method thereof | |
| CN106349746A (en) | Red reactive dye suitable for nylon dyeing and preparation method thereof | |
| CN101481525B (en) | Preparation of reactive red GN dye for fur | |
| CN102408747B (en) | A kind of red reactive dyes and preparation method thereof |
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 | ||
| CP02 | Change in the address of a patent holder |
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. |
|
| CP02 | Change in the address of a patent holder | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20230131 Granted publication date: 20140430 |
|
| PP01 | Preservation of patent right |