CN101705013B - Dark blue dye for dyeing nylon and preparation method thereof - Google Patents
Dark blue dye for dyeing nylon and preparation method thereof Download PDFInfo
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- CN101705013B CN101705013B CN 200910228254 CN200910228254A CN101705013B CN 101705013 B CN101705013 B CN 101705013B CN 200910228254 CN200910228254 CN 200910228254 CN 200910228254 A CN200910228254 A CN 200910228254A CN 101705013 B CN101705013 B CN 101705013B
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Abstract
The invention relates a dark blue dye for dyeing nylon and a preparation method thereof. The dye has a structural formula (I). The method for preparing the dye comprises the following steps: (a) adding solution of hydrochloric acid solution and solution of sodium nitrite into meta(para)-nitroaniline to obtain diazonium liquor; (b) dripping an H acid into the diazonium liquor obtained by the step (a) to perform reaction to obtain acid coupling liquor; (c) dissolving o-methoxyaniline meta-ester in water to obtain solution of o-methoxyaniline meta-ester; (d) adding the solution of o-methoxyaniline meta-ester obtained by the step (c) into cyanuric chloride suspension perform reaction, and adding 2,4-diaminobenzene sulfonic acid when the reaction is finished; (e) adding the solution of hydrochloric acid and the solution of the sodium nitrite into condensation reaction liquor obtained by the step (d) to obtain the diazonium liquor; (f) dripping the diazonium liquor obtained by the step (e) into the acid coupling liquor obtained by the step (b) to obtain alkaline coupling liquor; and (g) converting beta-sulfate ethyl sulfone of the coupling liquor obtained by the step (f) into vinylsulfonyl under an alkaline condition so as to obtain compounds of the structural formula (I), wherein R1 represents H and R2 represents NO2; or R2 represents H, and R1 represents 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 RIPSTOP 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 RIPSTOP.Because the factor of environmental ecology restriction, to dye uptake, degree of fixation and the dyeing waste-water of dyestuff require increasingly high.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 ORTHO ANISIDINE:
Position ester between ORTHO ANISIDINE is dissolved in the water, gets position aqueous solution of ester between ORTHO ANISIDINE;
(d) condensation reaction:
A position aqueous solution of ester reacts between the ORTHO ANISIDINE of adding (c) step acquisition in the cyanuric chloride suspension liquid, adding 2 after reaction is accomplished, 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 compound that the ethene sulfuryl has so just prepared said structure formula (I) (f) step.
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 ORTHO ANISIDINE:
Position ester between ORTHO ANISIDINE is dissolved in the water, regulates pH=3.5-4.0.
(d) condensation reaction:
In the cyanuric chloride suspension liquid, add the solution that (c) step obtains, 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, the adjustment 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, and adjustment 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 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 following:
2, the 4-diamino benzene sulfonic acid is the compound of following structure formula V:
The position ester is the compound of following structural formula (VI) between ORTHO ANISIDINE:
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 and 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 filtrating, collect filter cake, filtrating is discharging after treatment; Filter cake is dissolved in water, joins in the solid-liquid separator and separate, remove waste residue; Collection is filtrated in storage tank, and the waste residue that obtains in this step can be used for engineering soil;
(i) adjustment coloured light and intensity:
The filtrating that (h) step obtains is dry with small-sized spray 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, and 210 ℃ of adjustment inlet temperatures are carried out spraying drying with 95-100 ℃ temperature out, obtain dark blue dye of the present invention.
Used raw material all can be bought from 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.Compound method of the present invention can reduce environmental pollution, 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, further specify technical scheme of the present invention with embodiment below, but do not limit protection scope of the present invention.
Embodiment
The compound for preparing following structural formula (VII)
(a) in reaction kettle, add end water, add 13.8 kilograms of p-Nitroaniline, stirring and dissolving adds quantitative 30% hydrochloric acid soln; 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 ℃; Reacted 2 hours, and eliminated excessive nitrous acid, get diazonium liquid with thionamic acid.
(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) in reaction kettle, add end water, the position ester is 30.5 kilograms between the adding ORTHO ANISIDINE, and stirring and dissolving is transferred pH=3.5-4.0 with sodium bicarbonate, and making mass/volume (g/ml) concentration is 15%, obtains position ester solution between ORTHO ANISIDINE.
(d) in reaction kettle, add water of a small amount of end, add rubble ice, add 17.7 kilograms of cyanuric chlorides again, position ester solution between the ORTHO ANISIDINE that 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, 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 ℃; Reacted 2 hours, and eliminated excessive nitrous acid, get diazonium liquid with thionamic acid.
(f) be the acid coupling liquid of (b) step adjustment temperature 25 ℃, 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, the adjustment temperature is 10 ℃, adds 30% sodium hydroxide solution, and adjustment pH=9-9.5 kept 2 hours, adjusted pH=6-7 with 30% hydrochloric acid soln then.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 and filtrate in storage tank, obtain 1.5 kilograms of left and right sides waste residues and be used as engineering soil.
(i) filtrating that (h) step is obtained is dry with small-sized spray tower, and the adjustment of coloured light and intensity is carried out in dyeing again according to coloration result.
(k) the look liquid with (i) step joins in the feed liquid preheating container, and 210 ℃ of adjustment inlet temperatures are carried 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 following:
Compound of the present invention and preparation method thereof is described through concrete 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 all to be regarded as and are included 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) m-nitraniline or p-Nitroaniline diazotization reaction:
In m-nitraniline or p-Nitroaniline, add hydrochloric acid soln, 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 ORTHO ANISIDINE:
Position ester between ORTHO ANISIDINE is dissolved in the water, gets position aqueous solution of ester between ORTHO ANISIDINE;
(d) condensation reaction:
A position aqueous solution of ester reacts between the ORTHO ANISIDINE of adding (c) step acquisition in the cyanuric chloride suspension liquid, adding 2 after reaction is accomplished, 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) m-nitraniline or p-Nitroaniline diazotization reaction:
In the solution of m-nitraniline or p-Nitroaniline, add hydrochloric acid soln, 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 ORTHO ANISIDINE:
Position ester between ORTHO ANISIDINE is dissolved in the water, regulates pH=3.5-4.0;
(d) condensation reaction:
In the cyanuric chloride suspension liquid, add the solution that (c) step obtains, 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, the adjustment 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, and adjustment 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 and 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 filtrating, collect filter cake, filtrating is discharging after treatment; Filter cake is dissolved in water, joins in the solid-liquid separator and separate, remove waste residue; Collection is filtrated in storage tank, and the waste residue that obtains in this step can be used for engineering soil;
(i) adjustment coloured light and intensity:
The filtrating that (h) step obtains is dry with small-sized spray 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, and 210 ℃ of adjustment inlet temperatures are carried out spraying drying with 95-100 ℃ temperature out, obtain the dark blue dye of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910228254 CN101705013B (en) | 2009-11-16 | 2009-11-16 | Dark blue dye for dyeing nylon and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910228254 CN101705013B (en) | 2009-11-16 | 2009-11-16 | Dark blue dye for dyeing nylon and preparation method thereof |
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|---|---|
| CN101705013A CN101705013A (en) | 2010-05-12 |
| CN101705013B true CN101705013B (en) | 2012-12-19 |
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| CN114958026B (en) * | 2022-05-30 | 2023-05-23 | 金华双宏化工有限公司 | Improved trisazo red acid dye and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0022265A2 (en) * | 1979-07-06 | 1981-01-14 | Sumitomo Chemical Company, Limited | Reactive bisazo dyes, a process for their production and their use for dyeing cellulose fibers and cellulosic textiles |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0022265A2 (en) * | 1979-07-06 | 1981-01-14 | Sumitomo Chemical Company, Limited | Reactive bisazo dyes, a process for their production and their use for dyeing cellulose fibers and cellulosic textiles |
Non-Patent Citations (4)
| Title |
|---|
| JP昭56-128380A 1981.10.07 |
| JP昭57-167462A 1982.10.15 |
| JP昭59-133261A 1984.07.31 |
| JP昭60-99170A 1985.06.03 |
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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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