CN103030997B - Reactive red dye - Google Patents
Reactive red dye Download PDFInfo
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- CN103030997B CN103030997B CN201010266313.3A CN201010266313A CN103030997B CN 103030997 B CN103030997 B CN 103030997B CN 201010266313 A CN201010266313 A CN 201010266313A CN 103030997 B CN103030997 B CN 103030997B
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Abstract
The invention relates to a reactive red dye. The dye is a compound having a structure represented by formula (I). The preparation method of the dye comprises the following steps: 1, adding a meta-ester 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-amino-4'-nitrodiphenylamine, 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 obtain 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 preparation method of nylon active dyestuff.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:
Between a position ester solution join in cyanuric chloride solution reaction and obtain primary condensation liquid, then in this condensated liquid, add J acid, obtain secondary condensated liquid;
B, diazotization reaction:
In amino-the 4 '-nitrodiphenylamine of 4-, 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:
Position ester solution between 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 amino-the 4 '-nitrodiphenylamine of low temperature 4-, 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 a position ester, use NaHCO
3be neutralized to pH=2-5, position ester solution between obtaining; In reactor, add a small amount of water and a small amount of trash ice, then add cyanuric chloride, in stirring, position ester solution between dropping, 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 amino-the 4 '-nitrodiphenylamine of end water and 4-, 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;
The structure of its interposition ester is as follows:
The structure of cyanuric chloride is as follows:
The structure of J acid is as follows:
The structure of amino-the 4 '-nitrodiphenylamine of 4-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 a position ester 30Kg, use in NaHCO3 and pH=4-5, position ester solution between obtaining; In reactor, add a small amount of water and a small amount of trash ice, then add cyanuric chloride 19Kg, in stirring, position ester between dropping, T=10-15 ℃, 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.
Amino-the 4 '-nitrodiphenylamine diazotization of b, 4-:
In reactor, add amino-the 4 '-nitrodiphenylamine 23.2Kg of end water, 4-, 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. a kind of 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:
Between a position ester solution join in cyanuric chloride solution reaction and obtain primary condensation liquid, then in this condensated liquid, add J acid, obtain secondary condensated liquid;
B, diazotization reaction:
In amino-the 4 '-nitrodiphenylamine of 4-, 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:
Position ester solution between 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 amino-the 4 '-nitrodiphenylamine of low temperature 4-, 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 a position ester, with NaHCO3, be neutralized to pH=2-5, position ester solution between obtaining; In reactor, add a small amount of water and a small amount of trash ice, then add cyanuric chloride, in stirring, position ester solution between dropping, 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 amino-the 4 '-nitrodiphenylamine of end water and 4-, 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 |
|---|---|---|---|
| CN201010266313.3A CN103030997B (en) | 2010-08-30 | 2010-08-30 | Reactive red dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010266313.3A CN103030997B (en) | 2010-08-30 | 2010-08-30 | Reactive red dye |
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| CN103030997A CN103030997A (en) | 2013-04-10 |
| CN103030997B true CN103030997B (en) | 2014-04-30 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB923887A (en) * | 1959-03-24 | 1963-04-18 | Ici Ltd | New monoazo triazine dyestuffs |
| EP0115705A2 (en) * | 1982-12-28 | 1984-08-15 | Sumitomo Chemical Company, Limited | Monoazo compound having both monochlorotriazinyl and vinylsulfone type reactive groups |
| US5149791A (en) * | 1989-11-01 | 1992-09-22 | Ciba-Geigy Corporation | Chlorotriazine reactive dyes having a 4-methoxy-2-sulfoaniline diazo component and 2-amino-5-naphthol-7-sulfonic acid coupling component |
| US5324329A (en) * | 1992-06-26 | 1994-06-28 | Sumitomo Chemical Company, Limited | Reactive dye composition and dyeing or printing process 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 |
| CN101760041A (en) * | 2009-11-16 | 2010-06-30 | 天津德凯化工股份有限公司 | Active navy blue dye |
-
2010
- 2010-08-30 CN CN201010266313.3A patent/CN103030997B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB923887A (en) * | 1959-03-24 | 1963-04-18 | Ici Ltd | New monoazo triazine dyestuffs |
| EP0115705A2 (en) * | 1982-12-28 | 1984-08-15 | Sumitomo Chemical Company, Limited | Monoazo compound having both monochlorotriazinyl and vinylsulfone type reactive groups |
| JP2540598B2 (en) * | 1988-06-07 | 1996-10-02 | 日本化薬株式会社 | Reactive dye and dyeing method using the same |
| US5149791A (en) * | 1989-11-01 | 1992-09-22 | Ciba-Geigy Corporation | Chlorotriazine reactive dyes having a 4-methoxy-2-sulfoaniline diazo component and 2-amino-5-naphthol-7-sulfonic acid coupling component |
| US5324329A (en) * | 1992-06-26 | 1994-06-28 | Sumitomo Chemical Company, Limited | Reactive dye composition and dyeing or printing process using the same |
| CN101760041A (en) * | 2009-11-16 | 2010-06-30 | 天津德凯化工股份有限公司 | Active navy blue dye |
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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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