CN101709157B - Reactive navy blue dye suitable for nylon dyeing - Google Patents
Reactive navy blue dye suitable for nylon dyeing Download PDFInfo
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Abstract
The invention relates to a reactive navy blue dye suitable for nylon dyeing, which has the following structural formula (I). A preparation method for the dye comprises the following steps: (a) adding solution of hydrochloric acid and solution of sodium nitrite into p-(m-)nitroaniline to prepare diazo solution; (b) adding H acid into the diazo solution in the step (a) for reaction to prepare acid coupling solution; (c) dissolving 2,5-dimethoxy para-ester into water to prepare solution of 2,5-dimethoxy para-ester; (d) adding the solution of 2,5-dimethoxy para-ester obtained in the step (c) into aqueous solution of cyanuric chloride to react, and then adding p-phenylenediamine; (e) adding the solution of hydrochloric acid into condensation reaction solution in the step (d), and adding the solution of sodium nitrite into the mixture to prepare the diazo solution; (f) dripping the diazo solution in the step (e) into the acid coupling solution in the step (b) to prepare alkaline coupling solution; and (g) converting beta-sulfuric acid ester ethyl sulfone of the alkaline coupling solution obtained in the step (f) into vinylsulphonyl under the alkaline condition so as to prepare a compound with 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 () 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) preparation 2,5-dimethoxy para-ester solution:
2,5-dimethoxy para-ester is dissolved in the water, obtains 2, the 5-dimethoxy para-ester aqueous solution;
(d) condensation reaction:
Add 2 of (c) step acquisition in the water-soluble suspension of cyanuric chloride, the 5-dimethoxy para-ester aqueous solution reacts, and adds Ursol D after reaction is completed, and obtains 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 molten dropping liquid of H acid is added in the diazo liquid of (a) step, controls temperature of reaction at 5-15 ℃, reaction 4-8 hour, obtain acid coupling liquid.
(c) preparation 2,5-dimethoxy para-ester solution:
2,5-dimethoxy para-ester is dissolved in the water, regulates pH=3.5-4.0.
(d) condensation reaction:
The solution that adds (c) step to obtain in the water-soluble suspension of cyanuric chloride, the maintenance temperature is 0-15 ℃, pH=2.5-3.0, dropwise and keep reaction 4-6 hour, then add Ursol D, 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, has 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):
To () N-methyl-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:
2,5-dimethoxy para-ester (No. CAS: 21635-69-8) 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 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%, 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, add 33.4 kilograms of 2,5-dimethoxy para-esters, stirring and dissolving, transfer pH=3.5-4.0 with sodium bicarbonate, and making mass/volume (g/ml) concentration is 15%, obtains 2,5-dimethoxy para-ester solution.
(d) add water of a small amount of end in reactor, add rubble ice, then add 17.7 kilograms of cyanuric chlorides, drip in stirring that (c) step obtains 2,5-dimethoxy para-ester solution, keeping temperature is 5 ℃, pH=2.5-3.0, dropwise and keep reaction 5 hours, add 10.4 kilograms of Ursol D in solution, 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, dropwise and 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 like this 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）
R wherein
2For H, R
1For NO
2.
2. the preparation method of the dyestuff of claim 1, the method comprises the steps:
(a) p-Nitroaniline diazotization reaction:
Add hydrochloric acid soln in 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;
H acid is 1-amino-8-naphthol-3, the 6-disulfonate sodium, and it is the compound of following structural formula (III):
(c) preparation 2,5-dimethoxy para-ester solution:
2,5-dimethoxy para-ester is dissolved in the water, obtains 2, the 5-dimethoxy para-ester aqueous solution;
(d) condensation reaction:
Add 2 of (c) step acquisition in the cyanuric chloride aqueous solution, the 5-dimethoxy para-ester aqueous solution reacts, and adds Ursol D after reaction is completed, and obtains 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 drop-wise 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 alkaline coupling liquid of (f) step acquisition, so just prepared the compound of said structure formula (I).
3. method according to claim 2, the method comprises the steps:
(a) p-Nitroaniline diazotization reaction:
Add hydrochloric acid soln in the solution of 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;
H acid is 1-amino-8-naphthol-3, the 6-disulfonate sodium, and it is the compound of following structural formula (III):
(c) preparation 2,5-dimethoxy para-ester solution:
2,5-dimethoxy para-ester is dissolved in the water, regulates pH=3.5-4.0;
(d) condensation reaction:
The solution that adds (c) step to obtain in the water-soluble suspension of cyanuric chloride, the maintenance temperature is 0-15 ℃, pH=2.5-3.0, dropwise and keep reaction 4-6 hour, then add Ursol D, 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, has 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 % 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 is 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102282478A CN101709157B (en) | 2009-11-16 | 2009-11-16 | Reactive navy blue dye suitable for nylon dyeing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102282478A CN101709157B (en) | 2009-11-16 | 2009-11-16 | Reactive navy blue dye suitable for nylon dyeing |
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| CN101709157A CN101709157A (en) | 2010-05-19 |
| CN101709157B true CN101709157B (en) | 2013-11-13 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4622390A (en) * | 1980-09-06 | 1986-11-11 | Hoechst Aktiengesellschaft | Water-soluble disazo compounds containing an amino naphthol-disulfonic acid moiety as a coupling component and fibre-reactive groups |
| CN1580132A (en) * | 2003-08-15 | 2005-02-16 | 上海染料化工八厂 | Blue dye composition preparation and use |
| CN1934195A (en) * | 2004-03-19 | 2007-03-21 | 亨斯迈先进材料（瑞士）有限公司 | Mixtures of reactive dyes and their use |
| CN101368008A (en) * | 2007-08-15 | 2009-02-18 | 上海雅运纺织化工有限公司 | Navy blue reactive dye composition and dyeing uses in fibrous material thereof |
-
2009
- 2009-11-16 CN CN2009102282478A patent/CN101709157B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4622390A (en) * | 1980-09-06 | 1986-11-11 | Hoechst Aktiengesellschaft | Water-soluble disazo compounds containing an amino naphthol-disulfonic acid moiety as a coupling component and fibre-reactive groups |
| CN1580132A (en) * | 2003-08-15 | 2005-02-16 | 上海染料化工八厂 | Blue dye composition preparation and use |
| CN1934195A (en) * | 2004-03-19 | 2007-03-21 | 亨斯迈先进材料（瑞士）有限公司 | Mixtures of reactive dyes and their use |
| CN101368008A (en) * | 2007-08-15 | 2009-02-18 | 上海雅运纺织化工有限公司 | Navy blue reactive dye composition and dyeing uses in fibrous material thereof |
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| CN101709157A (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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