CN102433025A - Black active dye and preparation method thereof - Google Patents
Black active dye and preparation method thereof Download PDFInfo
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- CN102433025A CN102433025A CN2011102934892A CN201110293489A CN102433025A CN 102433025 A CN102433025 A CN 102433025A CN 2011102934892 A CN2011102934892 A CN 2011102934892A CN 201110293489 A CN201110293489 A CN 201110293489A CN 102433025 A CN102433025 A CN 102433025A
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- 0 Cc(cccc1)c1N=N[C@](C(*)C=C1C=C2*)C(O)=C1C(N)=C2N=Nc1cc(C)c(*)cc1* Chemical compound Cc(cccc1)c1N=N[C@](C(*)C=C1C=C2*)C(O)=C1C(N)=C2N=Nc1cc(C)c(*)cc1* 0.000 description 2
Abstract
The invention relates to a black active dye and a preparation method thereof, wherein the active dye has the following general structural formula (I); the invention further provides a preparation method of the active dye with the structural general formula (I). The black active dye prepared by the invention has high degree of colour development, high extent of reaction with fibres and high fixation rate; and the preparation method reduces environmental pollution, particularly the pollution of heavy metals.
Description
Technical field
The present invention relates to the reactive dyestuffs field, particularly a kind of pure cotton dyeing and painted black and active dye 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 painted black and active dye of cotton wool blending fabric and preparation method thereof of being applicable to is provided.
The technical scheme that the present invention adopts is:
A kind of black and active dye, these reactive dyestuffs have the general structure as shown in the formula (I):
Wherein
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 (II)
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 solution 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 solution; Be little blueness after potassium iodide starch paper soaks, T=0-10 ℃, reacted 1-3 hour; Eliminate excessive nitrous acid with sulfamic 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 (II)
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 preferred ORTHO AMINO PHENOL SULPHONIC sodium of the compound of structural formula (II), as follows:
Preferably, these reactive dyestuffs have following 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 of being mentioned among the present invention 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 the pollution of heavy metal.
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
A kind of black and active dye has the structural formula of formula (III):
The preparation method of formula (III) dye composition comprises the steps:
A. the diazotization reaction of O-methoxy para-ester:
In reactor, add entry; Add O-methoxy para-ester 180Kg dissolving, add 30% hydrochloric acid solution, add rubble ice again; Make that mass/volume concentration is 12% in its solution; Add 30% sodium nitrite solution again, make PH＜2 in the reaction solution, be little blueness after potassium iodide starch paper soaks; T=0-5 ℃; Reacted 2 hours, and eliminated excessive nitrous acid, get O-methoxy para-ester diazonium liquid with sulfamic acid;
B. acid coupling reaction
With H acid 205Kg,, make its whole dissolvings with in 30% sodium hydroxide solution and pH=6.0-7.0.Be added dropwise in the O-methoxy para-ester diazonium liquid that step a makes, control T=0-5 ℃, reacted 10 hours, acid coupling liquid;
C. ORTHO AMINO PHENOL SULPHONIC sodium diazotization reaction:
In reaction kettle, add entry, add ORTHO AMINO PHENOL SULPHONIC sodium 220Kg, stirring and dissolving adds 30% hydrochloric acid soln; Add rubble ice again, make that mass/volume concentration is 12% in its solution, add 30% sodium nitrite solution again, make pH＜2 in the reaction soln; After soaking, starch potassium iodide paper is little blueness, and T=0-5 ℃, reacted 2 hours, eliminate excessive nitrous acid with thionamic acid; Make ORTHO AMINO PHENOL SULPHONIC sodium diazonium liquid, treat alkaline coupling
D. alkaline coupling reaction
Adjust 20-25 ℃ of temperature to the acid coupling liquid that step b makes; The ORTHO AMINO PHENOL SULPHONIC sodium diazonium liquid that step c is made joins in the acid coupling liquid that step b makes, and transfers the pH=6.5-7.0 of solution with soda ash, is incubated 3.0 hours; The TLC plate is confirmed; Treat aftertreatment after qualified, get alkaline coupling liquid, get the dye solution of structural formula (III).
E removes insolubles: the alkaline coupling liquid that the d step is obtained joins in the solid-liquid separator and separates, and removes waste residue, collects filtrating,
F. adjust 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 removes 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, 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 (6)
1. black and active dye, it is characterized in that: these reactive dyestuffs have the general structure as shown in the formula (I):
Wherein
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. black and active dye according to claim 1 is characterized in that: the structural formula of these reactive dyestuffs is:
3. the preparation method of the described black and active dye 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;
(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 (II)
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 black and active dye 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 solution 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 solution; Be little blueness after potassium iodide starch paper soaks, T=0-10 ℃, reacted 1-3 hour; Eliminate excessive nitrous acid with sulfamic 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 (II)
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 4 described black and active dyes, it is characterized in that: the compound of said structural formula (II) is an ORTHO AMINO PHENOL SULPHONIC sodium:
6. the described black and active dye of claim 1 is used to dye cotton textiles or the painted purposes of cotton wool blending fabric.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102934892A CN102433025A (en) | 2011-09-29 | 2011-09-29 | Black active dye and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102934892A CN102433025A (en) | 2011-09-29 | 2011-09-29 | Black active dye and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073917A (en) * | 2012-12-31 | 2013-05-01 | 浙江瑞华化工有限公司 | Black reactive dye composition |
| CN103087549A (en) * | 2012-12-31 | 2013-05-08 | 浙江瑞华化工有限公司 | Novel active dark blue dye and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0315299B2 (en) * | 1981-07-27 | 1991-02-28 | Furukawa Denki Kogyo Kk | |
| CN1990605A (en) * | 2005-12-27 | 2007-07-04 | 明德国际仓储贸易(上海)有限公司 | Navy blue quaternary ammonium salt bisazo chemically-reactive dyes |
| CN101967303A (en) * | 2010-09-15 | 2011-02-09 | 天津德凯化工股份有限公司 | Reactive navy blue dye and preparation method thereof |
-
2011
- 2011-09-29 CN CN2011102934892A patent/CN102433025A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0315299B2 (en) * | 1981-07-27 | 1991-02-28 | Furukawa Denki Kogyo Kk | |
| CN1990605A (en) * | 2005-12-27 | 2007-07-04 | 明德国际仓储贸易(上海)有限公司 | Navy blue quaternary ammonium salt bisazo chemically-reactive dyes |
| CN101967303A (en) * | 2010-09-15 | 2011-02-09 | 天津德凯化工股份有限公司 | Reactive navy blue dye and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073917A (en) * | 2012-12-31 | 2013-05-01 | 浙江瑞华化工有限公司 | Black reactive dye composition |
| CN103087549A (en) * | 2012-12-31 | 2013-05-08 | 浙江瑞华化工有限公司 | Novel active dark blue dye and preparation method thereof |
| CN103073917B (en) * | 2012-12-31 | 2014-09-03 | 浙江瑞华化工有限公司 | Black reactive dye composition |
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Application publication date: 20120502 |