CN101812245B - Dark blue dye for dyeing nylon - Google Patents
Dark blue dye for dyeing nylon Download PDFInfo
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- CN101812245B CN101812245B CN 200910228248 CN200910228248A CN101812245B CN 101812245 B CN101812245 B CN 101812245B CN 200910228248 CN200910228248 CN 200910228248 CN 200910228248 A CN200910228248 A CN 200910228248A CN 101812245 B CN101812245 B CN 101812245B
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- 0 *c1cc(O)c2c(N)cc(S(O)(=O)=O)cc2c1 Chemical compound *c1cc(O)c2c(N)cc(S(O)(=O)=O)cc2c1 0.000 description 1
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Abstract
The invention relates to a dark blue dye for dyeing nylon. The dye has the following structural formula (I). A preparation method for the dye comprises the following steps: (a) adding hydrochloric acid solution and sodium nitrite solution into meta-nitroaniline or p-nitroaniline; (b) dripping H acid into the solution of the step (a); (c) dissolving o-anisidine meta-ester into water; (d) adding the solution obtained in the step (c) into cyanuric chloride suspension, and adding p-phenylenediamine into the solution after the reaction is finished; (e) adding the hydrochloric acid solution into the reaction solution of the step (d), and then adding sodium nitrite solution into the reaction solution; (f) dripping the solution of the step (e) into the solution of the step (b); and (g) converting beta-ethyl sulfone sulfate of the coupling solution of the step (f) into vinyl sulfone under the alkali condition so as to form a 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 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 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
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 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) 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:
Add that between the ORTHO ANISIDINE that (c) step obtains, a position aqueous solution of ester reacts in the cyanuric chloride suspension liquid, add Ursol D after reaction is completed, get condensation reaction solution;
(e) diazotization reaction:
Add hydrochloric acid soln in the condensation reaction solution of (d) step, then add 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, then add 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, controls temperature of reaction at 5-15 ℃, reacted 4-8 hour, get 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:
The solution that adds (c) step to obtain 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:
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 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 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; 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:
Ursol D is the compound of following structure formula V:
Between ORTHO ANISIDINE, position ester (CAS:10079-20-6) is 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 separate in 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 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, carries out spraying drying with the temperature out of 95-100 ℃, 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 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 illustrates 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) 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, 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 between ORTHO ANISIDINE 30.5 kilograms of position esters, 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) 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 the ORTHO ANISIDINE that in stirring, dropping (c) step obtains, 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 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 solid-liquid separator, 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.
(k) the look liquid with (i) step joins in the feed liquid preheating container, adjusts 210 ℃ of inlet temperatures, carries out spraying drying with the temperature out of 95-100 ℃., 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)
2. the preparation method of the dyestuff of claim 1, the method comprises the steps:
(a) m-nitraniline or p-Nitroaniline diazotization reaction:
Add hydrochloric acid soln in m-nitraniline or 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) 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:
Add that between the ORTHO ANISIDINE that (c) step obtains, a position aqueous solution of ester reacts in the cyanuric chloride suspension liquid, add Ursol D after reaction is completed, get condensation reaction solution;
(e) diazotization reaction:
Add hydrochloric acid soln in the condensation reaction solution of (d) step, then add 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).
3. method according to claim 2, the method comprises the steps:
(a) m-nitraniline or p-Nitroaniline diazotization reaction:
Add hydrochloric acid soln in the solution of m-nitraniline or 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 ℃, 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, controls temperature of reaction at 5-15 ℃, reacted 4-8 hour, get 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: the solution that adds (c) step to obtain in the cyanuric chloride suspension liquid, keeping temperature is 0-15 ℃, pH=2.5-3.0, dropwise and keep 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;
(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 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 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).
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 separate in 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 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, carries out spraying drying with the temperature out of 95-100 ℃, obtains the dark blue dye of claim 1.
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CN 200910228248 CN101812245B (en) | 2009-11-16 | 2009-11-16 | Dark blue dye for dyeing nylon |
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CN 200910228248 CN101812245B (en) | 2009-11-16 | 2009-11-16 | Dark blue dye for dyeing nylon |
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CN101812245B true CN101812245B (en) | 2013-06-19 |
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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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JPS56128380A (en) * | 1980-03-14 | 1981-10-07 | Sumitomo Chemical Co | Dyeing of cellulosic fiber |
JPS57167462A (en) * | 1981-04-07 | 1982-10-15 | Sumitomo Chemical Co | Dyeing of cellulosic fiber |
JPS59133261A (en) * | 1983-01-19 | 1984-07-31 | Sumitomo Chem Co Ltd | Bifunctional reactive compound |
JPS6099170A (en) * | 1983-11-04 | 1985-06-03 | Mitsui Toatsu Chem Inc | Disazo-based reactive dye |
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Patent Citations (1)
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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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