CN102504581A - Extra-dark black active dye and preparation method thereof - Google Patents
Extra-dark black active dye and preparation method thereof Download PDFInfo
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- CN102504581A CN102504581A CN2011102974372A CN201110297437A CN102504581A CN 102504581 A CN102504581 A CN 102504581A CN 2011102974372 A CN2011102974372 A CN 2011102974372A CN 201110297437 A CN201110297437 A CN 201110297437A CN 102504581 A CN102504581 A CN 102504581A
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Abstract
The invention relates to an extra-dark black active dye and a preparation method thereof. The active dye has a structural general formula as a formula (I) in the specification. The invention also provides the preparation method of the dye in the formula (I). The dye has the advantages of high color development degree, high reaction degree with fiber and high color fixation rate; and the preparation method has the advantage of reducing environmental pollution, especially reducing pollution of heavy metals.
Description
Technical field
The present invention relates to the reactive dyestuffs field, particularly a kind of pure cotton dyeing and dark type black and active dye of the painted spy of cotton wool blending fabric and preparation method thereof of being applicable to.
Background technology
Reactive dyestuffs history is of short duration, but is expected most development prospect at present, becomes production and competitively develops, uses expansion day by day; Well received dye; Special dark type reactive dyestuffs are a kind of of current frontier nature product, during this dyeing, because the color development degree of color bodies is different; And must adapt between color bodies and the active group that just to reach the color development degree high; And, therefore develop the degree of fixation height at present to performance requriements and all progressively raisings of the environmental requirement in the production process of reactive dyestuffs, the special dark type reactive dyestuffs that dyeing process does not have waste water become development today trend.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of pure cotton dyeing and dark type black and active dye of the painted spy of cotton wool blending fabric and preparation method thereof of being applicable to is provided.
The technical scheme that the present invention adopts does
The dark type black and active dye of a kind of spy, these reactive dyestuffs have the general structure as shown in the formula (I):
In the formula (I)
R
1For-H or-SO
3Na or-OCH
3
R
2For-H or-SO
3Na or-OCH
3Or-CH
3
R
3For-SO
2C
2H
4OSO
3Na;
R
4For-H or-SO
3Na or-OH.
The present invention also provides the preparation method of the compound of above-mentioned formula (I), comprises the steps:
(a) diazotization reaction:
Any compound in the following structural formula (X-1) to (X-3) is dissolved in water, add hydrochloric acid soln then, add rubble ice; Add sodium nitrite solution again; Make pH＜2 in the reaction soln, be little blueness after potassium iodide starch paper soaks, react step (a) diazonium liquid;
(X-1) sulfonation para-ester
(X-2) O-methoxy para-ester
(X-3) gram Li Xiding para-ester
(b) acid coupling reaction
H acid is neutralized to pH=6.0-7.0 with sodium hydroxide solution, makes its whole dissolvings, join in step (a) the diazonium liquid, react acid coupling liquid;
(c) diazotization reaction:
The compound dissolution of following structural formula (II) in water, is stirred, hydrochloric acid soln is added, add rubble ice, add sodium nitrite solution again, make pH＜2.0 in the reaction soln, be little blueness after starch potassium iodide paper soaks, react step (c) diazonium liquid;
R in the formula
4For-H or-SO
3Na or-OH;
(d) alkaline coupling reaction
Step (c) diazonium liquid is joined in the acid coupling liquid that step (b) obtains, transfers the pH=5.5-7.0 of solution with soda ash, react alkaline coupling liquid; Promptly get dyestuff in the said structure formula (I).
Particularly, the preparation method of the compound of above-mentioned formula (I) comprises the steps:
(a) diazotization reaction:
Any compound in the following structural formula (X-1) to (X-3) is dissolved in water, add 30% hydrochloric acid soln then, add rubble ice; Make that mass/volume concentration is 10-15% in its solution, add 30% sodium nitrite solution again, make pH＜2 in the reaction soln; Be little blueness after potassium iodide starch paper soaks, T=0-10 ℃, reacted 1-3 hour; Eliminate excessive nitrous acid with thionamic acid, get step (a) diazonium liquid;
(X-1) sulfonation para-ester
(X-2) O-methoxy para-ester
(X-3) gram Li Xiding para-ester
(b) acid coupling reaction
H acid is neutralized to pH=6.0-7.0 with the 20%-40% sodium hydroxide solution, makes its whole dissolvings, join in step (a) the diazonium liquid, reacted 6-10 hour, get acid coupling liquid;
(c) diazotization reaction:
The compound dissolution of following structural formula (II) in water, is stirred, 30% hydrochloric acid soln is added; Add rubble ice, make that mass/volume concentration is 10-15% in its solution, add 30% sodium nitrite solution again; Make pH＜2.0 in the reaction soln, be little blueness after starch potassium iodide paper soaks, T=0-10 ℃; Reacted 1-3 hour, and eliminated excessive nitrous acid, get step (c) diazonium liquid with thionamic acid;
R in the formula
4For-H or-SO
3Na or-OH;
(d) alkaline coupling reaction
The acid coupling liquid adjustment temperature that obtains step (b) is 15-25 ℃, and step (c) diazonium liquid is joined in this acid coupling liquid, and the pH=5.5-7.0 with soda ash accent solution is incubated 1-3 hour, gets alkaline coupling liquid; Promptly get dye solution in the said structure formula (I).
Preferably, this preparation method also comprises the steps:
(e) remove insolubles: the alkaline coupling liquid that will (d) step obtains joins and separates in the solid-liquid separator, removes waste residue, and collect and filtrate,
(f). adjustment coloured light and intensity: the filtrating of (e) step 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,
(g) remove insolubles: the look liquid of (f) step is joined in the feed liquid preheating container, and 210 ℃ of adjustment inlet temperatures are carried out spraying drying with 95-100 ℃ temperature out, promptly obtain the dyestuff finished product of structural formula (I).
In the aforesaid method, the compound of structural formula (II) is preferably as follows (Y-1) structure,
Wherein the preparation method of structural formula (Y-1) compound comprises the steps:
In retort, add entry, add a para-ester or a position ester again, adjust T=15-40 ℃, use NaHCO
3Or Na2CO
3Transfer pH=7.0-7.5, get a para-ester solution or a position ester solution, treat a step condensation; In another retort, add ice, water and ice milling aid add cyanuric chloride then, make the material mixing, drip the para-ester solution or the position ester solution that make; Keep T=0-15 ℃, pH=2-5 dropwises, and reacts then 3-5 hour; The thing that contracts, contracting one adds 2,4-diamino benzene sulfonic acid sodium or 2,5-diamino benzene sulfonic acid sodium in the thing; Adjust T=15-40 ℃, pH=4-6 reacted 2-8 hour, made above-mentioned formula (Y-1) compound.
Preferably, the dark type black and active dye of a kind of spy has formula (III) structural formula.
The present invention also provides said structure formula (I) black and active dye to be used to dye cotton textiles or the painted purposes of cotton wool blending fabric.
The unit of the mass/volume concentration that summary of the invention part of the present invention and specific embodiment are partly mentioned is g/mL or kg/L.
The structural formula information of the compound that the present invention mentions is:
The para-ester chemistry is by name: to (beta-hydroxyethyl sulfone sulfate) aniline, structural formula is as follows:
Between bit esterified formal name used at school be :-structural formula of beta-hydroxyethyl sulfone sulfate ester aniline is:
The structural formula of cyanuric chloride is:
H acid is 1-amino-8-naphthol-3, the abbreviation of 6-disulfonate sodium, and its structural formula is following:
The beneficial effect that the present invention had:
The above-mentioned dyestuff that the present invention develops is the dark type reactive dyestuffs of a kind of spy, is the frontier nature product of current reactive dyestuffs.When above-mentioned dyestuff dyes dark color, because the color development degree of its color bodies is different, adapt between color bodies and the active group, the color development degree is high, and high with the fiber-reactive degree, degree of fixation is high, and the preparation method reduces environmental pollution, especially reduces heavy metal contamination.
Embodiment
In order to understand the present invention, further specify the present invention with embodiment below, but do not limit the present invention.
Embodiment 1
The dark type black and active dye of a kind of spy, these reactive dyestuffs have formula (III) structural formula.
The preparation method of formula (III) dye composition comprises the steps:
A. sulfonation para-ester diazotization reaction:
In reaction kettle, add entry, add sulfonation para-ester 340Kg, stirring and dissolving adds 30% hydrochloric acid soln; Add rubble ice, make that mass/volume concentration is 12% in its solution, add 30% sodium nitrite solution again, make PH＜2.0 in the reaction soln; Be little blueness after starch potassium iodide paper soaks, T=0-5 ℃, reacted 2 hours; Eliminate excessive nitrous acid with thionamic acid, treat acid coupling, get sulfonation para-ester diazonium liquid.
B. acid coupling reaction
With H acid 270Kg, be neutralized to pH=6.0-7.0 with 30% sodium hydroxide solution, make its whole dissolvings, be added dropwise in the sulfonation para-ester diazonium liquid that step a makes, control T=10-20 ℃, reacted 10 hours, must acid coupling liquid;
C. two the synthetic of thing that contract:
In 2 tons of retort, add entry 1000Kg, add para-ester 180Kg, adjust T=15-40 ℃, use NaHCO
3Transfer pH=7.0-7.5, get para-ester solution, treat a step condensation; In 5 tons of retort, add ice, water and ice milling aid add cyanuric chloride 200Kg then, make the material mixing; The para-ester solution that dropping makes keeps T=0-15 ℃, and pH=2-5 dropwises; Reacted then 5 hours, the thing that contracts, contracting one adds 2,5-diamino benzene sulfonic acid sodium 265Kg in the thing; Adjust T=15-40 ℃, pH=4-6 reacted 7 hours.The two thing solution that contract, laminate is analyzed the qualified diazotization reaction of treating.
D. two contract thing diazotization reaction
Two contract and add 30% hydrochloric acid in the thing solution to what step c made, add rubble ice, make that mass/volume concentration is 13% in its solution; Add 30% sodium nitrite solution again, make PH＜2.0 in the reaction soln, be little blueness after starch potassium iodide paper soaks; T=0-5 ℃, reacted 2 hours, eliminate excessive nitrous acid with thionamic acid; Treat alkaline coupling, the two thing diazonium liquid that contract;
E. alkaline coupling reaction
Adjust 15-25 ℃ of temperature to the acid coupling liquid that step b makes; The two thing diazonium drops that contract that steps d is made are added in the acid coupling liquid, transfer pH=5.5-7.0 with soda ash in the dropping, drip to finish to keep 2 hours; The TLC plate is confirmed; Treat aftertreatment after qualified, get alkaline coupling liquid, get dye solution shown in the formula (III);
F. remove insolubles: the alkaline coupling liquid that the e step is obtained joins in the solid-liquid separator and separates, and removes waste residue, collects filtrating,
G. adjust coloured light and intensity: the filtrating of f step 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,
H. remove insolubles: the look liquid of g step is joined in the feed liquid preheating container, and 210 ℃ of adjustment inlet temperatures are carried out spraying drying with 95-100 ℃ temperature out, obtain the dyestuff finished product.
The application performance table of the dyestuff of embodiments of the invention 1:
Method of the present invention 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 (7)
1. dark type black and active dye of spy, it is characterized in that: these reactive dyestuffs have the general structure as shown in the formula (I):
In the formula (I)
R
1For-H or-SO
3Na or-OCH
3
R
2For-H or-SO
3Na or-OCH
3Or-CH
3
R
3For-SO
2C
2H
4OSO
3Na;
R
4For-H or-SO
3Na or-OH.
2. the dark type black and active dye of a kind of spy according to claim 1 is characterized in that: these reactive dyestuffs have the structural formula as shown in the formula (III):
3. the preparation method of the dark type black and active dye of the described spy of claim 1 is characterized in that: comprise the steps:
(a) diazotization reaction:
Any compound in the following structural formula (X-1) to (X-3) is dissolved in water, add hydrochloric acid soln then, add rubble ice; Add sodium nitrite solution again; Make pH＜2 in the reaction soln, be little blueness after potassium iodide starch paper soaks, react step (a) diazonium liquid;
(b) acid coupling reaction
H acid is neutralized to pH=6.0-7.0 with sodium hydroxide solution, makes its whole dissolvings, join in step (a) the diazonium liquid, react acid coupling liquid;
(c) diazotization reaction:
The compound dissolution of following structural formula (II) in water, is stirred, hydrochloric acid soln is added, add rubble ice, add sodium nitrite solution again, make pH＜2.0 in the reaction soln, be little blueness after starch potassium iodide paper soaks, react step (c) diazonium liquid;
R in the formula
4For-H or-SO
3Na or-OH;
(d) alkaline coupling reaction
Step (c) diazonium liquid is joined in the acid coupling liquid that step (b) obtains, transfers the pH=5.5-7.0 of solution with soda ash, react alkaline coupling liquid; Promptly get dyestuff in the said structure formula (I).
4. the preparation method of the dark type black and active dye of spy according to claim 3 is characterized in that: comprise the steps:
(a) diazotization reaction:
Any compound in the following structural formula (X-1) to (X-3) is dissolved in water, add 30% hydrochloric acid soln then, add rubble ice; Make that mass/volume concentration is 10-15% in its solution, add 30% sodium nitrite solution again, make pH＜2 in the reaction soln; Be little blueness after potassium iodide starch paper soaks, T=0-10 ℃, reacted 1-3 hour; Eliminate excessive nitrous acid with thionamic acid, get step (a) diazonium liquid;
(b) acid coupling reaction
H acid is neutralized to pH=6.0-7.0 with the 20%-40% sodium hydroxide solution, makes its whole dissolvings, join in step (a) the diazonium liquid, reacted 6-10 hour, get acid coupling liquid;
(c) diazotization reaction:
The compound dissolution of following structural formula (II) in water, is stirred, 30% hydrochloric acid soln is added; Add rubble ice, make that mass/volume concentration is 10-15% in its solution, add 30% sodium nitrite solution again; Make pH＜2.0 in the reaction soln, be little blueness after starch potassium iodide paper soaks, T=0-10 ℃; Reacted 1-3 hour, and eliminated excessive nitrous acid, get step (c) diazonium liquid with thionamic acid;
R in the formula
4For-H or-SO
3Na or-OH;
(d) alkaline coupling reaction
The acid coupling liquid adjustment temperature that obtains step (b) is 15-25 ℃, and step (c) diazonium liquid is joined in this acid coupling liquid, and the pH=5.5-7.0 with soda ash accent solution is incubated 1-3 hour, gets alkaline coupling liquid; Promptly get dye solution in the said structure formula (I).
Preferably, this preparation method also comprises the steps:
(e) remove insolubles: the alkaline coupling liquid that will (d) step obtains joins and separates in the solid-liquid separator, removes waste residue, and collect and filtrate,
(f). adjustment coloured light and intensity: the filtrating of (e) step 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,
(g) remove insolubles: the look liquid of (f) step is joined in the feed liquid preheating container, and 210 ℃ of adjustment inlet temperatures are carried out spraying drying with 95-100 ℃ temperature out, promptly obtain the dyestuff finished product of structural formula (I).
5. according to the preparation method of claim 3 or the dark type black and active dye of 4 described spies, it is characterized in that: the compound of said structural formula (II) is (Y-1) structure as follows,
6. the preparation method of the dark type black and active dye of spy according to claim 5 is characterized in that: said structural formula (Y-1) compound is made by the method that comprises the steps:
In retort, add entry, add a para-ester or a position ester again, adjust T=15-40 ℃, use NaHCO
3Or Na
2CO
3Transfer pH=7.0-7.5, get a para-ester solution or a position ester solution, treat a step condensation; In another retort, add ice, water and ice milling aid add cyanuric chloride then, make the material mixing, drip the para-ester solution or the position ester solution that make; Keep T=0-15 ℃, pH=2-5 dropwises, and reacts then 3-5 hour; The thing that contracts, contracting one adds 2,4-diamino benzene sulfonic acid sodium or 2,5-diamino benzene sulfonic acid sodium in the thing; Adjust T=15-40 ℃, pH=4-6 reacted 2-8 hour, made above-mentioned formula (Y-1) compound.
7. claim 1 or 2 described black and active dyes are used to dye cotton textiles or the painted purposes of cotton wool blending fabric.
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| CN2011102974372A CN102504581A (en) | 2011-09-29 | 2011-09-29 | Extra-dark black active dye and preparation method thereof |
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| CN2011102974372A CN102504581A (en) | 2011-09-29 | 2011-09-29 | Extra-dark black active dye and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111759A (en) * | 2018-10-26 | 2019-01-01 | 天津德凯化工股份有限公司 | A kind of digital ink-jet printed active dark blue dye and preparation method thereof |
| CN109233334A (en) * | 2018-10-26 | 2019-01-18 | 天津德凯化工股份有限公司 | A kind of dark blue reactive dye |
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| US20010044527A1 (en) * | 2000-03-14 | 2001-11-22 | Clariant Finance (Bvi) Limited | Fiber-reactive disazo compounds |
| 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 |
| CN101555360A (en) * | 2009-05-06 | 2009-10-14 | 上海科华染料工业有限公司 | Active tricolor dye composition |
| CN102161838A (en) * | 2011-02-16 | 2011-08-24 | 刘鹏 | Composite active black dye |
| WO2011101185A1 (en) * | 2010-02-18 | 2011-08-25 | Huntsman Advanced Materials (Switzerland) Gmbh | Mixtures of fibre-reactive dyes and their use in a method for di- or trichromatic dyeing or printing |
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2011
- 2011-09-29 CN CN2011102974372A patent/CN102504581A/en active Pending
Patent Citations (6)
| 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 |
| US20010044527A1 (en) * | 2000-03-14 | 2001-11-22 | Clariant Finance (Bvi) Limited | Fiber-reactive disazo compounds |
| 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 |
| CN101555360A (en) * | 2009-05-06 | 2009-10-14 | 上海科华染料工业有限公司 | Active tricolor dye composition |
| WO2011101185A1 (en) * | 2010-02-18 | 2011-08-25 | Huntsman Advanced Materials (Switzerland) Gmbh | Mixtures of fibre-reactive dyes and their use in a method for di- or trichromatic dyeing or printing |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111759A (en) * | 2018-10-26 | 2019-01-01 | 天津德凯化工股份有限公司 | A kind of digital ink-jet printed active dark blue dye and preparation method thereof |
| CN109233334A (en) * | 2018-10-26 | 2019-01-18 | 天津德凯化工股份有限公司 | A kind of dark blue reactive dye |
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Application publication date: 20120620 |