CN101709158A - Reactive dye and preparation method thereof - Google Patents
Reactive dye and preparation method thereof Download PDFInfo
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- CN101709158A CN101709158A CN200910228251A CN200910228251A CN101709158A CN 101709158 A CN101709158 A CN 101709158A CN 200910228251 A CN200910228251 A CN 200910228251A CN 200910228251 A CN200910228251 A CN 200910228251A CN 101709158 A CN101709158 A CN 101709158A
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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 used dyestuff of the dyeing of nylon fabrics is weak acid dye and metallized dye.Because fabric that weak acid dye dyed, fastness is not good enough, and coloured light is not bright-coloured, the particularly pollution the when pollution of metallized dye heavy metal in manufacturing processed and dyeing, and the infringement that human skin is held up of painted nylon fabrics.Because it is 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 piecing together black.The invention provides a kind of active dark blue dye that is applicable to dyeing nylon, solved the painted technical problem of cellulosic fibre and tynex.
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
1Be H, R
2Be NO
2, perhaps R
2Be H, R
1Be 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 the N-methyl-p-nitroaniline, add sodium nitrite solution then, obtain diazonium liquid;
(b) acid coupling reaction:
The H acid solution is added drop-wise in the diazonium liquid that (a) step obtains reacts, acid coupling liquid;
(c) position ester solution between the preparation:
A position ester is dissolved in the water between inciting somebody to action, position aqueous solution of ester between getting;
(d) condensation reaction:
A position aqueous solution of ester reacted between adding (c) step obtained in the cyanuric chloride suspension liquid, added 2 after reaction is finished, and the 4-diamino benzene sulfonic acid gets condensation reaction solution;
(e) diazotization reaction:
In the condensation reaction solution of (d) step, add hydrochloric acid soln, add sodium nitrite solution again, get diazonium liquid;
(f) alkaline coupling reaction:
The diazonium drop of (e) step is joined in the acid coupling liquid of (b) step, get 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, add sodium nitrite solution again, guarantee reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, temperature is 0-35 ℃, reacts 1-3 hour, eliminate excessive Sodium Nitrite with thionamic acid then, get diazonium liquid;
(b) acid coupling reaction:
The H acid solution is added drop-wise in the diazonium liquid of (a) step, control reaction temperature was reacted 4-8 hour at 5-15 ℃, got acid coupling liquid.
(c) position ester solution between the preparation:
A position ester is dissolved in the water between inciting somebody to action, and regulates pH=3.5-4.0.
(d) condensation reaction:
Add the solution that (c) step obtains in the cyanuric chloride suspension liquid, keeping temperature is 0-15 ℃, and pH=2.5-3.0 dropwises maintenance reaction 4-6 hour, add 2 then, the 4-diamino benzene sulfonic acid, adjusting temperature is 10-40 ℃, pH=4-7 reacted 2-4 hour, got condensation reaction solution.
(e) diazotization reaction:
In the condensation reaction solution of (d) step, add hydrochloric acid soln, add sodium nitrite solution again, keep reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, keep 0-15 ℃ of temperature, reacted 1-3 hour, eliminate excessive nitrous acid with thionamic acid then, get diazonium liquid;
(f) alkaline coupling reaction:
The diazonium drop of (e) step is joined in the acid coupling liquid of (b) step, transfer pH=6-7 with soda ash in the dropping, dropwise maintenance reaction 1-2 hour, get alkaline coupling liquid;
(g) hydrolysis reaction
With the alkaline coupling liquid of trash ice adjustment (f) step temperature 10-15 ℃ adds sodium hydroxide solution, adjusts pH=9-9.5, keeps reaction 1-3 hour, adjusts pH=6-7 with hydrochloric acid soln then; 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 the aforesaid method:
Cyanuric chloride is the compound of following structural formula (II):
H acid is the amino 8-naphthols-3 of 1-, 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, the 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 the 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 weight %, and sodium nitrite solution is the sodium nitrite in aqueous solution of 30 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 joined separate in the solid-liquid separator, 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 the solid-liquid separator and separate, remove filtrate, collect filter cake, filtrate is discharged after treatment, filter cake is dissolved in water, joins in the 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 is obtained is with small-sized spray tower drying, and the adjustment of coloured light and intensity is carried out in dyeing again 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, carries out spraying drying with 95-100 ℃ temperature out, obtains dark blue dye of the present invention.
Used raw material all can be bought from the market and obtain in the aforesaid method.
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, improved dyeing quality greatly, reduced the usage quantity of dyestuff, but also eliminated the pollution of heavy metal environment.Synthetic method of the present invention can reduce environmental pollution, and the desired raw material cost is low, the product solubility height, 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, further specify technical scheme of the present invention with embodiment below, but do not limit protection scope of the present invention.
Embodiment
Be prepared as follows the compound of structural formula (VII)
(a) in reactor, add end water, add 13.8 kilograms of m-nitranilines, stirring and dissolving, quantitative 30% hydrochloric acid soln is added, add rubble ice, making its solution quality/volume (g/ml) concentration is 10%, adds 30% sodium nitrite solution again, in reaction process, keep pH value of solution＜2, be little blueness after starch potassium iodide paper soaks, keeping temperature is 15 ℃, reacts 2 hours, eliminate excessive nitrous acid with thionamic acid, get diazonium liquid.
(b) H acid is prepared into the aqueous solution for 32.7 kilograms, regulates pH value=6.8-7.2, be added drop-wise in the diazonium liquid of (a) step, keeping temperature is 10 ℃, reacts 6 hours, gets acid coupling liquid.
(c) add end water in reactor, the position ester is 27.5 kilograms between adding, and stirring and dissolving is transferred pH=3.5-4.0 with sodium bicarbonate, and making mass/volume (g/ml) concentration is 15%, position ester solution between obtaining.
(d) in reactor, add water of a small amount of end, add rubble ice, add 17.7 kilograms of cyanuric chlorides again, position ester solution between dropping (c) step obtains in the stirring, keeping temperature is 5 ℃, and pH=2.5-3.0 dropwises maintenance reaction 5 hours, in solution, add 2,18.0 kilograms of 4-diamino benzene sulfonic acids, keeping temperature is 30 ℃, pH=6, reacted 3 hours, and got condensated liquid.
(e) with the condensated liquid temperature of rubble ice adjustment (d) step, add 30% hydrochloric acid, add 30% sodium nitrite solution again, 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, get diazonium liquid.
(f) the acid coupling liquid of (b) step being adjusted temperature is 25 ℃, and the diazonium liquid that (e) step is obtained adds in this acid coupling liquid, transfers pH=6-7 with soda ash in the dropping, dropwises to keep 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 separate in the solid-liquid separator, remove waste residue, collect filtrate in storage tank, obtain 1.5 kilograms of left and right sides waste residues and be used as engineering soil.
(i) filtrate that (h) step is obtained is dyeed with small-sized spray tower drying, carries out the adjustment of coloured light and intensity again according to coloration result.
(j) the look liquid with (i) step joins in the feed liquid preheating container, adjusts 210 ℃ of inlet temperatures, carries out spraying drying with 95-100 ℃ temperature out., the finished product after obtaining handling.
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 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 regarded as comprising within the 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):
Wherein, R
1Be H, R
2Be NO
2, perhaps R
2Be H, R
1Be NO
2
2. the preparation method of the dyestuff of claim 1, this method comprises the steps:
(a) (to) the N-methyl-p-nitroaniline diazotization reaction:
To (to) add hydrochloric acid soln in the N-methyl-p-nitroaniline, add sodium nitrite solution then, obtain diazonium liquid;
(b) acid coupling reaction:
The H acid solution is added drop-wise in the diazonium liquid that (a) step obtains reacts, acid coupling liquid;
(c) position ester solution between the preparation:
A position ester is dissolved in the water between inciting somebody to action, position aqueous solution of ester between getting;
(d) condensation reaction:
A position aqueous solution of ester reacted between adding (c) step obtained in the cyanuric chloride suspension liquid, added 2 after reaction is finished, and the 4-diamino benzene sulfonic acid gets condensation reaction solution;
(e) diazotization reaction:
In the condensation reaction solution of (d) step, add hydrochloric acid soln, add sodium nitrite solution again, get diazonium liquid;
(f) alkaline coupling reaction:
The diazonium drop of (e) step is joined in the acid coupling liquid of (b) step, get 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, this method 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, add sodium nitrite solution again, guarantee reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, temperature is 0-35 ℃, reacts 1-3 hour, eliminate excessive Sodium Nitrite with thionamic acid then, get diazonium liquid;
(b) acid coupling reaction:
The H acid solution is added drop-wise in the diazonium liquid of (a) step, control reaction temperature was reacted 4-8 hour at 5-15 ℃, got acid coupling liquid.
(c) position ester solution between the preparation:
A position ester is dissolved in the water between inciting somebody to action, and regulates pH=3.5-4.0.
(d) condensation reaction:
Add the solution that (c) step obtains in the cyanuric chloride suspension liquid, keeping temperature is 0-15 ℃, and pH=2.5-3.0 dropwises maintenance reaction 4-6 hour, add 2 then, the 4-diamino benzene sulfonic acid, adjusting temperature is 10-40 ℃, pH=4-7 reacted 2-4 hour, got condensation reaction solution.
(e) diazotization reaction:
In the condensation reaction solution of (d) step, add hydrochloric acid soln, add sodium nitrite solution again, keep reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, keep 0-15 ℃ of temperature, reacted 1-3 hour, eliminate excessive nitrous acid with thionamic acid then, get diazonium liquid;
(f) alkaline coupling reaction:
The diazonium drop of (e) step is joined in the acid coupling liquid of (b) step, transfer pH=6-7 with soda ash in the dropping, dropwise maintenance reaction 1-2 hour, get alkaline coupling liquid;
(g) hydrolysis reaction
With the alkaline coupling liquid of trash ice adjustment (f) step temperature 10-15 ℃ adds sodium hydroxide solution, adjusts pH=9-9.5, keeps reaction 1-3 hour, adjusts pH=6-7 with hydrochloric acid soln then; 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).
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 weight %, and sodium nitrite solution is the sodium nitrite in aqueous solution of 30 weight %.
6. according to claim 2 or 3 described methods, this method also comprises the post-processing step of product, and post-processing step comprises:
(h) remove insolubles:
The product of (g) step joined separate in the solid-liquid separator, 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 the solid-liquid separator and separate, remove filtrate, collect filter cake, filtrate is discharged after treatment, filter cake is dissolved in water, joins in the 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 is obtained is with small-sized spray tower drying, and the adjustment of coloured light and intensity is carried out in dyeing again 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, carries out spraying drying with 95-100 ℃ temperature out, obtains dark blue dye of the present invention.
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| CN2009102282514A CN101709158B (en) | 2009-11-16 | 2009-11-16 | Reactive dye and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142753A (en) * | 2017-06-05 | 2017-09-08 | 西安工程大学 | Response type levelling agent and preparation method and application |
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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142753A (en) * | 2017-06-05 | 2017-09-08 | 西安工程大学 | Response type levelling agent and preparation method and application |
| CN107142753B (en) * | 2017-06-05 | 2019-12-10 | 西安工程大学 | Reactive leveling agent and preparation method and application thereof |
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| CN101709158B (en) | 2013-11-13 |
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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 |