CN101709155B - Reactive navy blue dye and preparation method thereof - Google Patents
Reactive navy blue dye and preparation method thereof Download PDFInfo
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- CN101709155B CN101709155B CN 200910228244 CN200910228244A CN101709155B CN 101709155 B CN101709155 B CN 101709155B CN 200910228244 CN200910228244 CN 200910228244 CN 200910228244 A CN200910228244 A CN 200910228244A CN 101709155 B CN101709155 B CN 101709155B
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Abstract
The invention relates to a reactive navy blue dye and a preparation method thereof, wherein the dye has the following structural formula (I), and the preparation method of the dye comprises the following steps of: a. adding a hydrochloric acid solution and a sodium nitrite solution into meta(para)-nitroaniline to obtain a diazo liquid; b. dropwise adding an H acid into the diazo liquid obtained in the step a for reaction to obtain an acidic coupling liquid; c. dissolving para-ester into water to obtain a para-ester solution; d. adding the para-ester solution obtained in the step c into a cyanuric chloride suspension for reaction, and adding para-phenylene diamine after the reaction is finished; e. adding the hydrochloric acid solution into a condensation reaction liquid obtained in the step d, and then adding the sodium nitrite solution to obtain the diazo liquid; f. dropwise adding the diazo liquid obtained in the step e into the acidic coupling liquid obtained in the step b to obtain an alkaline coupling liquid; and g. transforming beta-sulfuric ester ethyl sulfone into vinyl sulfuryl under an alkaline condition of the coupling liquid obtained in the step f, thereby preparing a compound with the structural formula (I), wherein R1 is H and R2 is NO2, or R2 is H and R1 is NO2.
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 the fabric that dyes of weak acid dye, fastness is not good enough, and coloured light is not bright-coloured, the infringement that the particularly pollution the when pollution of metallized dye heavy metal in manufacturing processed and dyeing, and the nylon fabrics that dyes is held up human skin.Because the environmental ecology restricting factor, 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 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
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, 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 reacts, get acid coupling liquid;
(c) preparation para-ester solution:
Para-ester is dissolved in the water, gets the para-ester aqueous solution;
(d) condensation reaction:
Add the para-ester aqueous solution that (c) step obtains in the cyanuric chloride suspension liquid and react, adding Ursol D after reaction is finished gets condensation reaction solution;
(e) diazotization reaction:
In the condensation reaction solution of (d) step, add hydrochloric acid soln, add again sodium nitrite solution, get diazo liquid;
(f) alkaline coupling reaction:
The diazo liquid of (e) step is added dropwise in the acid coupling liquid of (b) step, gets 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 again sodium nitrite solution, guarantee reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, temperature is 0-35 ℃, reacts 1-3 hour, then eliminate excessive Sodium Nitrite with thionamic acid, get diazo liquid;
(b) acid coupling reaction:
The H acid solution is added drop-wise in the diazo liquid of (a) step, the control temperature of reaction was reacted 4-8 hour at 5-15 ℃, got acid coupling liquid.
(c) preparation para-ester solution:
Para-ester is dissolved in the water, 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 ℃, pH=2.5-3.0, dropwise maintenance reaction 4-6 hour, then add Ursol D, 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 again sodium nitrite solution, keep reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, keep 0-15 ℃ of temperature, reacted 1-3 hour, then eliminate excessive nitrous acid with thionamic acid, get 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 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, then adjusts pH=6-7 with hydrochloric acid soln; 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 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:
Ursol D is the compound of following structure formula V:
Para-ester is 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 % 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 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 obtains is dry with the small spraying tower, 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.
In the aforesaid method used raw material all be 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 of the present invention can environmental contamination reduction, and the desired raw material cost is low, and 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, the below further specifies technical scheme of the present invention with embodiment, but does 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 p-Nitroaniline, stirring and dissolving, 30% quantitative 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 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, gets acid coupling liquid.
(c) add end water in reactor, add 27.5 kilograms of para-esters, stirring and dissolving is transferred pH=3.5-4.0 with sodium bicarbonate, and making mass/volume (g/ml) concentration is 15%, obtains para-ester solution.
(d) in reactor, add water of a small amount of end, add rubble ice, add again 17.7 kilograms of cyanuric chlorides, drip the para-ester solution that (c) step obtains in the stirring, keeping temperature is 5 ℃, pH=2.5-3.0 dropwises maintenance reaction 5 hours, adds 10.4 kilograms of Ursol D in solution, keeping temperature is 30 ℃, pH=6 reacted 3 hours, got 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, get 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 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 dry with the small spraying tower, and the adjustment of coloured light and intensity is carried out in dyeing 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 processing.
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, 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 (5)
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, the method comprises the steps:
(a) m-nitraniline or p-Nitroaniline diazotization reaction:
In the solution of m-nitraniline or p-Nitroaniline, add hydrochloric acid soln, add again sodium nitrite solution, guarantee reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, temperature is 0-35 ℃, reacts 1-3 hour, then eliminate excessive nitrous acid with thionamic acid, get diazo liquid;
(b) acid coupling reaction:
The H acid solution is added drop-wise in the diazo liquid of (a) step, the control temperature of reaction was reacted 4-8 hour at 5-15 ℃, got 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):
(c) preparation para-ester solution:
Para-ester is dissolved in the water, regulates pH=3.5-4.0,
Para-ester is the compound of following structural formula (VI):
(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, then add Ursol D, adjusting temperature is 10-40 ℃, pH=4-7, reacted 2-4 hour, and got condensation reaction solution
Cyanuric chloride is the compound of following structural formula (II):
(e) diazotization reaction:
In the condensation reaction solution of (d) step, add hydrochloric acid soln, add again sodium nitrite solution, keep reaction soln pH＜2, be little blueness after starch potassium iodide paper soaks, keep 0-15 ℃ of temperature, reacted 1-3 hour, then eliminate excessive nitrous acid with thionamic acid, get 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 the dropping, dropwise maintenance reaction 1-2 hour, get alkaline coupling liquid;
(g) hydrolysis reaction
Temperature with the alkaline coupling liquid of trash ice adjustment (f) step is 10-15 ℃, adds sodium hydroxide solution, adjusts pH=9-9.5, keeps reaction 1-3 hour, then adjusts pH=6-7 with hydrochloric acid soln; Wherein sodium hydroxide solution is 30% sodium hydroxide solution, and hydrochloric acid soln is 30% hydrochloric acid soln; Get the compound of structural formula (I).
3. method according to claim 2, wherein the H acid solution in (b) step is the aqueous solution, its pH value=6.8-7.2.
4. method according to claim 2, 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.
5. method according to claim 2, the 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 is used for engineering soil;
(i) adjust coloured light and intensity:
The filtrate that (h) step obtains is dry with the small spraying tower, 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 the dark blue dye of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910228244 CN101709155B (en) | 2009-11-16 | 2009-11-16 | Reactive navy blue dye and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910228244 CN101709155B (en) | 2009-11-16 | 2009-11-16 | Reactive navy blue dye and preparation method thereof |
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| CN101709155A CN101709155A (en) | 2010-05-19 |
| CN101709155B true CN101709155B (en) | 2013-03-20 |
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| CN 200910228244 Active CN101709155B (en) | 2009-11-16 | 2009-11-16 | Reactive navy blue dye and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4412948A (en) * | 1979-07-06 | 1983-11-01 | Sumitomo Chemical Company, Limited | Reactive disazo blue dye |
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2009
- 2009-11-16 CN CN 200910228244 patent/CN101709155B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4412948A (en) * | 1979-07-06 | 1983-11-01 | Sumitomo Chemical Company, Limited | Reactive disazo blue dye |
Non-Patent Citations (4)
| Title |
|---|
| JP平3-261641A 1991.11.21 |
| JP昭56-128380A 1981.10.07 |
| JP昭57-167462A 1982.10.15 |
| JP昭59-133261A 1984.07.31 |
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| CN101709155A (en) | 2010-05-19 |
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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: 20130320 |