CN101709158B - Reactive dye and preparation method thereof - Google Patents
Reactive dye and preparation method thereof Download PDFInfo
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- CN101709158B CN101709158B CN2009102282514A CN200910228251A CN101709158B CN 101709158 B CN101709158 B CN 101709158B CN 2009102282514 A CN2009102282514 A CN 2009102282514A CN 200910228251 A CN200910228251 A CN 200910228251A CN 101709158 B CN101709158 B CN 101709158B
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Abstract
The invention relates to a reactive dye and a preparation method thereof. The dye has the following structural formula (I). The preparation method of the dye is as follows: (a) adding hydrochloric acid solution and sodium nitrite solution into meta nitro aniline (paranitroaniline) to obtain heavy nitrogen liquid; (b) dropwise adding H acid into the heavy nitrogen liquid obtained in step (a) to react so as to obtain acidic coupling liquid; (c) dissolving meta-ester into water to obtain meta-ester solution; (d) adding the meta-ester solution obtained in step (c) into cyanuric chloride suspension to react, and adding 2,4-diaminobenzenesulphonic acid after reaction is finished; (e) adding hydrochloric acid solution to condensation reaction liquid obtained in step (d), and then adding sodium nitrite solution to obtain the heavy nitrogen liquid; (f) dropwise adding the heavy nitrogen liquid obtained in step (e) into the acidic coupling liquid obtained in step (b); and (g) converting the acidic coupling liquid obtained in step (f) by beta-sulfate ethyl sulfone into vinylsulfony under alkali condition to prepare the compound of the structural formula (I).
Description
Technical field
The present invention relates to the dye well its preparation method, particularly, the present invention relates to a kind of active dark blue dye and preparation method thereof.
Background technology
The general dyestuff used of the dyeing of nylon fabrics is weak acid dye and metallized dye.Due to the fabric that weak acid dye dyes, fastness is not good enough, and coloured light is not bright-coloured, the infringement that the particularly pollution in the pollution of metallized dye heavy metal in manufacturing processed and when dyeing, and the nylon fabrics that dyes is held up mankind's skin.Due to the factor of environmental ecology restriction, more and more higher to the requirement of dye uptake, degree of fixation and the dyeing waste-water of dyestuff.The exploitation of the active nylon dyestuff of navy is the focus of dye industry always, and this is because navy consumption in all tones is maximum, and is the main ingredient of spelling black.The invention provides a kind of active dark blue dye that is applicable to dyeing nylon, solved the technical problem of cellulosic fibre and tynex dyeing.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of active dark blue dye that is applicable to dyeing nylon, this dyestuff has following structural formula (I):
Wherein, R
1For H, R
2For NO
2, perhaps R
2For H, R
1For NO
2
The preparation method of said structure formula (I) compound dyestuff comprises the steps:
(a) (to) the N-methyl-p-nitroaniline diazotization reaction:
To (to) add hydrochloric acid soln in N-methyl-p-nitroaniline, then add sodium nitrite solution, obtain diazo liquid;
(b) acid coupling reaction:
The H acid solution is added drop-wise in the diazo liquid that (a) step obtains and reacts, obtain acid coupling liquid;
(c) position ester solution between the preparation:
Between inciting somebody to action, a position ester is dissolved in the water, position aqueous solution of ester between obtaining;
(d) condensation reaction:
React to a position aqueous solution of ester between adding that (c) step obtains in the cyanuric chloride suspension liquid, add 2,4-diamino benzene sulfonic acid after reaction is completed, obtain condensation reaction solution;
(e) diazotization reaction:
Add hydrochloric acid soln in the condensation reaction solution of (d) step, then add sodium nitrite solution, obtain diazo liquid;
(f) alkaline coupling reaction:
The diazo liquid of (e) step is added dropwise in the acid coupling liquid of (b) step, obtains alkaline coupling liquid;
(g) hydrolysis reaction
Under alkaline condition, make its beta-sulfuric ester ethyl sulfonyl be converted into the ethene sulfuryl (f) step, so just prepared the compound of said structure formula (I).
More specifically, the preparation method of said structure formula (I) compound dyestuff comprises the steps:
(a) (to) the N-methyl-p-nitroaniline diazotization reaction:
(to) add hydrochloric acid soln in the solution of N-methyl-p-nitroaniline, then add sodium nitrite solution, guarantee reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, temperature is 0-35 ℃, reaction 1-3 hour, then eliminate excessive Sodium Nitrite with thionamic acid, obtain diazo liquid;
(b) acid coupling reaction:
The H acid solution is added drop-wise in the diazo liquid of (a) step, controls temperature of reaction at 5-15 ℃, reaction 4-8 hour, obtain acid coupling liquid.
(c) position ester solution between the preparation:
Between inciting somebody to action, a position ester is dissolved in the water, and regulates pH=3.5-4.0.
(d) condensation reaction:
The solution that adds (c) step to obtain in the cyanuric chloride suspension liquid, the maintenance temperature is 0-15 ℃, pH=2.5-3.0 dropwises and keeps reaction 4-6 hour, then add 2,4-diamino benzene sulfonic acid, the adjustment temperature is 10-40 ℃, pH=4-7, reaction 2-4 hour, obtain condensation reaction solution.
(e) diazotization reaction:
Add hydrochloric acid soln in the condensation reaction solution of (d) step, then add sodium nitrite solution, keep reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, keep temperature 0-15 ℃, reaction 1-3 hour, then eliminate excessive nitrous acid with thionamic acid, obtain diazo liquid;
(f) alkaline coupling reaction:
The diazo liquid of (e) step is added dropwise in the acid coupling liquid of (b) step, transfers pH=6-7 with soda ash in dropping, dropwise and keep reaction 1-2 hour, obtain alkaline coupling liquid;
(g) hydrolysis reaction
Temperature 10-15 ℃ with the alkaline coupling liquid of trash ice adjustment (f) step, add sodium hydroxide solution, adjusts pH=9-9.5, keeps reaction 1-3 hour, then with hydrochloric acid soln, adjusts pH=6-7; Wherein sodium hydroxide solution is 30% sodium hydroxide solution, and hydrochloric acid soln is 30% hydrochloric acid soln;
So just prepared the compound of said structure formula (I).
In aforesaid method:
Cyanuric chloride is the compound of following structural formula (II):
H acid is 1-amino-8-naphthol-3, the 6-disulfonate sodium, and it is the compound of following structural formula (III):
P-Nitroaniline is the compound of following structural formula (IV):
The structure of m-nitraniline is as follows:
2,4-diamino benzene sulfonic acid is the compound of following structure formula V:
Between the position ester be the compound of following structural formula (VI):
In aforesaid method,
Preferably, the H acid solution is the aqueous solution, its pH value=6.8-7.2;
Preferably, (e) hydrochloric acid soln in the step is the aqueous hydrochloric acid of 30 % by weight, and sodium nitrite solution is the sodium nitrite in aqueous solution of 30 % by weight.
Preferably, above-mentioned preparation method can also comprise the post-processing step of product, and post-processing step can be selected as required, and post-processing step comprises:;
(h) remove insolubles:
The product of (g) step is joined in solid-liquid separator and separates, remove waste residue, collect filtrate in storage tank;
Perhaps sodium-chlor or Repone K are joined in the product of (g) step according to a certain percentage, stirred 1 hour, join in solid-liquid separator and separate, remove filtrate, collect filter cake, filtrate is discharged after treatment, filter cake is dissolved in water, joins in solid-liquid separator and separate, remove waste residue, collect filtrate in storage tank, the waste residue that obtains in this step can be used for engineering soil;
(i) adjust coloured light and intensity:
The filtrate that (h) step obtains is dry with the small spraying tower, dyeing, then carry out the adjustment of coloured light and intensity according to coloration result;
(j) drying:
The look liquid that (i) step is obtained joins in the feed liquid preheating container, adjusts 210 ℃ of inlet temperatures, with the temperature out of 95-100 ℃, carries out spraying drying, obtains dark blue dye of the present invention.
In aforesaid method raw material used be all can purchase from the market available.
Active dark blue dye of the present invention has not only that good boldness, degree of fixation, lifting force and colouring are even, dye yield is high, also have the consistency good with other reactive dyestuffs, greatly improved dyeing quality, reduce the usage quantity of dyestuff, but also eliminated the pollution of heavy metal to environment.Synthetic method energy environmental contamination reduction of the present invention, the desired raw material cost is low, product solubility is high, and bright in colour, application performance is excellent, easy to use, is applicable to cotton, especially dyeing nylon.
Embodiment
, in order to understand the present invention, below with embodiment, further illustrate technical scheme of the present invention, but do not limit the scope of the invention.
Embodiment
Be prepared as follows the compound of structural formula (VII)
(a) add end water in reactor, add 13.8 kilograms of m-nitranilines, stirring and dissolving, 30% quantitative hydrochloric acid soln is added, add rubble ice, making its solution quality/volume (g/ml) concentration is 1 0%, then adds 30% sodium nitrite solution, keep pH value of solution＜2 in reaction process, be little blueness after starch potassium iodide paper soaks, keeping temperature is 15 ℃, reacts 2 hours, eliminate excessive nitrous acid with thionamic acid, obtain diazo liquid.
(b) 32.7 kilograms of H acid are prepared into the aqueous solution, regulate pH value=6.8-7.2, be added drop-wise in the diazo liquid of (a) step, keeping temperature is 10 ℃, reacts 6 hours, obtains acid coupling liquid.
(c) add end water in reactor, between adding, the position ester is 27.5 kilograms, and stirring and dissolving, transfer pH=3.5-4.0 with sodium bicarbonate, and making mass/volume (g/ml) concentration is 15%, position ester solution between obtaining.
(d) add water of a small amount of end in reactor, add rubble ice, then add 17.7 kilograms of cyanuric chlorides, position ester solution between in stirring, dropping (c) step obtains, keeping temperature is 5 ℃, and pH=2.5-3.0 dropwises and keeps reaction 5 hours, add 2 in solution, 18.0 kilograms of 4-diamino benzene sulfonic acids, keeping temperature is 30 ℃, pH=6, reacted 3 hours, and obtained condensated liquid.
(e) with the condensated liquid temperature of rubble ice adjustment (d) step, add 30% hydrochloric acid, add again 30% sodium nitrite solution, keep reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, keeping temperature is 5 ℃, reacts 2 hours, eliminate excessive nitrous acid with thionamic acid, obtain diazo liquid.
(f) the acid coupling liquid of (b) step being adjusted temperature is 25 ℃, and the diazo liquid that (e) step is obtained adds in this acid coupling liquid, transfers pH=6-7 with soda ash in dropping, dropwises and keeps reaction 1 hour.
(g) rubble ice is joined in the product that (f) step obtains, adjusting temperature is 10 ℃, adds 30% sodium hydroxide solution, adjusts pH=9-9.5, keeps 2 hours, then with 30% hydrochloric acid soln adjustment pH=6-7.Obtain the compound of structural formula (VII).
Post-processing step:
(h) (g) step solution is joined in solid-liquid separator and separates, remove waste residue, collect filtrate in storage tank, obtain 1.5 kilograms of left and right waste residues and be used as engineering soil.
(i) filtrate that (h) step is obtained is dry with the small spraying tower, dyeing, then carry out the adjustment of coloured light and intensity according to coloration result.
(j) the look liquid of (i) step is joined in the feed liquid preheating container, adjusts 210 ℃ of inlet temperatures, with the temperature out of 95-100 ℃, carry out spraying drying., the finished product after being processed.
The performance table of the nylon active dark blue dye of the structural formula that embodiment prepares (VII) is as follows:
Compound of the present invention and preparation method 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, within all similar replacements and change will become apparent to those skilled in the art that and all be deemed to be included in scope of the present invention.
Claims (6)
1. active dark blue dye that is applicable to dyeing nylon, this dyestuff has following structural formula (I):
（I）
Wherein, R
1For H, R
2For NO
2
2. the preparation method of the dyestuff of claim 1, the method comprises the steps:
(a) m-nitraniline diazotization reaction:
Add hydrochloric acid soln in m-nitraniline, then add sodium nitrite solution, obtain diazo liquid;
(b) acid coupling reaction:
The H acid solution is added drop-wise in the diazo liquid that (a) step obtains and reacts, obtain acid coupling liquid;
H acid is 1-amino-8-naphthol-3, the 6-disulfonate sodium, and it is the compound of following structural formula (III):
（III）
(c) position ester solution between the preparation:
Between inciting somebody to action, a position ester is dissolved in the water, position aqueous solution of ester between obtaining;
(d) condensation reaction:
React to a position aqueous solution of ester between adding that (c) step obtains in the cyanuric chloride suspension liquid, add 2,4-diamino benzene sulfonic acid after reaction is completed, obtain condensation reaction solution;
(e) diazotization reaction:
Add hydrochloric acid soln in the condensation reaction solution of (d) step, then add sodium nitrite solution, obtain diazo liquid;
(f) alkaline coupling reaction:
The diazo liquid of (e) step is added dropwise in the acid coupling liquid of (b) step, obtains alkaline coupling liquid;
(g) hydrolysis reaction
Under alkaline condition, make its beta-sulfuric ester ethyl sulfonyl be converted into the ethene sulfuryl (f) step, so just prepared the compound of said structure formula (I).
3. method according to claim 2, the method comprises the steps:
(a) m-nitraniline diazotization reaction:
Add hydrochloric acid soln in the solution of m-nitraniline, then add sodium nitrite solution, guarantee reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, temperature is 0-35 ℃, reaction 1-3 hour, then eliminate excessive Sodium Nitrite with thionamic acid, obtain diazo liquid;
(b) acid coupling reaction:
The H acid solution is added drop-wise in the diazo liquid of (a) step, controls temperature of reaction at 5-15 ℃, reaction 4-8 hour, obtain acid coupling liquid;
H acid is 1-amino-8-naphthol-3, the 6-disulfonate sodium, and it is the compound of following structural formula (III):
（III）
(c) position ester solution between the preparation:
Between inciting somebody to action, a position ester is dissolved in the water, and regulates pH=3.5-4.0;
(d) condensation reaction:
The solution that adds (c) step to obtain in the cyanuric chloride suspension liquid, the maintenance temperature is 0-15 ℃, pH=2.5-3.0 dropwises and keeps reaction 4-6 hour, then add 2,4-diamino benzene sulfonic acid, the adjustment temperature is 10-40 ℃, pH=4-7, reaction 2-4 hour, obtain condensation reaction solution;
(e) diazotization reaction:
Add hydrochloric acid soln in the condensation reaction solution of (d) step, then add sodium nitrite solution, keep reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, keep temperature 0-15 ℃, reaction 1-3 hour, then eliminate excessive nitrous acid with thionamic acid, obtain diazo liquid;
(f) alkaline coupling reaction:
The diazo liquid of (e) step is added dropwise in the acid coupling liquid of (b) step, transfers pH=6-7 with soda ash in dropping, dropwise and keep reaction 1-2 hour, obtain alkaline coupling liquid;
(g) hydrolysis reaction
Temperature 10-15 ℃ with the alkaline coupling liquid of trash ice adjustment (f) step, add sodium hydroxide solution, adjusts pH=9-9.5, keeps reaction 1-3 hour, then with hydrochloric acid soln, adjusts pH=6-7; Wherein sodium hydroxide solution is 30% sodium hydroxide solution, and hydrochloric acid soln is 30% hydrochloric acid soln;
So just prepared the compound of claim 1 structural formula (I).
4. according to claim 2 or 3 described methods, wherein the H acid solution in (b) step is the aqueous solution, its pH value=6.8-7.2.
5. according to claim 2 or 3 described methods, wherein the hydrochloric acid soln in (e) step is the aqueous hydrochloric acid of 30 % by weight, sodium nitrite solution is the sodium nitrite in aqueous solution of 30 % by weight.
6. according to claim 2 or 3 described methods, the method also comprises the post-processing step of product, and post-processing step comprises:
(h) remove insolubles:
The product of (g) step is joined in solid-liquid separator and separates, remove waste residue, collect filtrate in storage tank;
Perhaps sodium-chlor or Repone K are joined in the product of (g) step according to a certain percentage, stirred 1 hour, join in solid-liquid separator and separate, remove filtrate, collect filter cake, filtrate is discharged after treatment, filter cake is dissolved in water, joins in solid-liquid separator and separate, remove waste residue, collect filtrate in storage tank, the waste residue that obtains in this step can be used in engineering soil;
(i) adjust coloured light and intensity:
The filtrate that (h) step obtains is dry with the small spraying tower, dyeing, then carry out the adjustment of coloured light and intensity according to coloration result;
(j) drying:
The look liquid that (i) step is obtained joins in the feed liquid preheating container, adjusts 210 ℃ of inlet temperatures, with the temperature out of 95-100 ℃, carries out spraying drying, obtains the dark blue dye of claim 1.
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| CN2009102282514A CN101709158B (en) | 2009-11-16 | 2009-11-16 | Reactive dye and preparation method thereof |
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|---|---|---|---|
| CN2009102282514A CN101709158B (en) | 2009-11-16 | 2009-11-16 | Reactive dye and preparation method thereof |
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| CN101709158B true CN101709158B (en) | 2013-11-13 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1751103A (en) * | 2003-02-21 | 2006-03-22 | 日本化药株式会社 | Reactive dye composition and method of dyeing with the same |
| CN1768118A (en) * | 2003-04-01 | 2006-05-03 | 西巴特殊化学品控股有限公司 | Mixtures of reactive dyes and their use |
| CN101027363A (en) * | 2004-09-29 | 2007-08-29 | 亨斯迈先进材料（瑞士）有限公司 | Reactive dyes, their preparation and their use |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1751103A (en) * | 2003-02-21 | 2006-03-22 | 日本化药株式会社 | Reactive dye composition and method of dyeing with the same |
| CN1768118A (en) * | 2003-04-01 | 2006-05-03 | 西巴特殊化学品控股有限公司 | Mixtures of reactive dyes and their use |
| CN101027363A (en) * | 2004-09-29 | 2007-08-29 | 亨斯迈先进材料（瑞士）有限公司 | Reactive dyes, their preparation and their use |
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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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Effective date of registration: 20230131 Granted publication date: 20131113 |