CN102433026A - Black active dye for pure cotton or cotton and wool blended textile dyeing and preparation method thereof - Google Patents

Black active dye for pure cotton or cotton and wool blended textile dyeing and preparation method thereof Download PDF

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CN102433026A
CN102433026A CN2011102972343A CN201110297234A CN102433026A CN 102433026 A CN102433026 A CN 102433026A CN 2011102972343 A CN2011102972343 A CN 2011102972343A CN 201110297234 A CN201110297234 A CN 201110297234A CN 102433026 A CN102433026 A CN 102433026A
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add
acid
solution
liquid
ester
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张兴华
李荣才
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Tianjin Dek Chemical Co Ltd
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Tianjin Dek Chemical Co Ltd
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Abstract

The invention relates to a black active dye for pure cotton or cotton and wool blended textile dyeing 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 compound with the structural formula (I). The dye of 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.

Description

Cotton textiles or the dyeing of cotton wool blending fabric are with black and active dye and preparation method thereof
Technical field
The present invention relates to the reactive dyestuffs field, particularly a kind of pure cotton dyeing or 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):
Figure BDA0000096044830000011
Wherein
R 1For-H or-SO 3M or-OCH 3
R 2For-H or-SO 3M or-SO 2C 2H 4OSO 3M or-CH 3Or-OCH 3Or
Figure BDA0000096044830000012
R 3For-H or-SO 3M or-SO 2C 2H 4OSO 3M;
R 4For-H or-SO 3M or-OH;
R5 is-H
Or
Figure BDA0000096044830000021
Figure BDA0000096044830000022
M is-K or-Na; Preferably, M is-Na;
And structural formula (I) does not comprise substituent R 1, R 2, R 3, R 4, R 5, M is the compound of following structure:
R 1For-H or-SO 3M or-OCH 3R 2For-H or-SO 3M or-CH 3Or-OCH 3
R 3For-H or-SO 3M; R 4For-H or-SO 3M or-OH; R 5For-H; M is-K or-Na.
Preferably, in the formula (I)
R 1For-H or-SO 3M or-OCH 3
R 2For-H or-SO 3M or-CH 3Or-OCH 3
R 3For-SO 2C 2H 4OSO 3M;
R 4For-H or-SO 3M or-OH;
R 5For
Figure BDA0000096044830000023
Figure BDA0000096044830000024
M is-Na.
Preferably, in the formula (I)
R 1For-H or-SO 3M or-OCH 3
R 2For-SO 2C 2H 4OSO 3M or
Figure BDA0000096044830000031
Or
Figure BDA0000096044830000032
R 3For-H or-SO 3M;
R 4For-H or-SO 3M or-OH;
R 5For
Figure BDA0000096044830000033
M is-Na.
The present invention also provides the preparation method of the compound of said structure formula (I), comprises the steps:
(a) diazotization reaction:
Any compound in the following structural formula (X-1) to (X-8) 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;
Figure BDA0000096044830000035
Figure BDA0000096044830000041
(X-3) aniline-2, the 5-disulfonic acid
Figure BDA0000096044830000042
(X-4) sulfonation para-ester
(X-5) O-methoxy para-ester
Figure BDA0000096044830000044
(X-6) position ester between O-methoxy
Figure BDA0000096044830000045
(X-7) 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;
Figure BDA0000096044830000051
R wherein 4, R 5Implication isostructure general formula (I)
(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 said structure formula (I) comprises the steps:
(a) diazotization reaction:
Any compound in the following structural formula (X-1) to (X-8) 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;
Figure BDA0000096044830000061
(X-3) aniline-2, the 5-disulfonic acid
(X-4) sulfonation para-ester
Figure BDA0000096044830000063
(X-5) O-methoxy para-ester
Figure BDA0000096044830000064
(X-6) position ester between O-methoxy
Figure BDA0000096044830000065
(X-7) gram Li Xiding para-ester.
Figure BDA0000096044830000071
(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;
Figure BDA0000096044830000072
R wherein 4, R 5Implication isostructure general formula (I).
(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, any compound among the compound of structural formula (II) preferred (X-1), (X-2), (Y-1), (Y-2), (Y-3).
Figure BDA0000096044830000073
Figure BDA0000096044830000081
Figure BDA0000096044830000082
(Y-2) ORTHO AMINO PHENOL SULPHONIC sodium
Figure BDA0000096044830000083
In the above-mentioned chemical formula, wherein the contract preparation method of thing of (X-1) two comprises the steps:
Figure BDA0000096044830000084
In retort, add entry, add para-ester again, adjust T=15-40 ℃, use NaHCO 3Or Na 2CO 3Transfer pH=7.0-7.5, get para-ester solution, treat a step condensation; In another retort, add ice, water and ice milling aid add cyanuric chloride then, make the material mixing; The para-ester solution that dropping makes keeps T=0-15 ℃, and pH=2-5 dropwises; Reacted then 3-5 hour, the thing that contracts, contracting one adds 2,4-diamino benzene sulfonic acid sodium in the thing; Adjust T=15-40 ℃, pH=4-6 reacted 2-8 hour, made above-mentioned (X-1) two thing that contracts.
In the above-mentioned chemical formula, wherein the contract preparation method of thing of (X-2) two comprises the steps:
Figure BDA0000096044830000091
In retort, add entry, add the Monoethanolamine MEA BASF sulfuric ester, adjust T=15-40 ℃, use NaHCO 3Transfer pH=5.0-6.5, get Monoethanolamine MEA BASF sulfuric ester solution, treat a step condensation, in another retort, add ice, water and ice milling aid; Add cyanuric chloride then, behind the mixing, drip Monoethanolamine MEA BASF sulfuric ester solution, keep T=0-15 ℃, pH=2-5; Dropwise, reacted then 3-5 hour, the thing that contracts, contracting one then adds 2,4-diamino benzene sulfonic acid sodium in the thing; Adjust T=15-40 ℃, pH=5-8, reaction times 4-7 hour, chromatography detected, (X-2) two thing that contracts;
In the above-mentioned chemical formula, wherein the contract preparation method of thing of (Y-1) comprises the steps:
Figure BDA0000096044830000092
In retort, add entry, add 2,5-diamino benzene sulfonic acid sodium adjust temperature T=0-5 ℃, adds 2,3-two bromo propionyl chloros, and 4 hours reaction times, finish, thing must (Y-1) contracts.
In the above-claimed cpd, wherein (Y-3) two preparation method of thing that contracts comprises the steps:
Figure BDA0000096044830000093
In retort, add entry, add para-ester again, adjust T=15-40 ℃, use NaHCO 3Or Na 2CO 3Transfer pH=7.0-7.5, get para-ester solution, treat a step condensation; In another retort, add ice, water and ice milling aid add cyanuric chloride then, make the material mixing; The para-ester solution that dropping makes keeps T=0-15 ℃, and pH=2-5 dropwises; Reacted then 3-5 hour, the thing that contracts, contracting one adds 2,5-diamino benzene sulfonic acid sodium in the thing; Adjust T=15-40 ℃, pH=4-6 reacted 2-8 hour, made above-mentioned (Y-3) two thing that contracts.
Preferably, the volume percent of the ice milling aid that the present invention mentions consists of dioxane 30%, diethylolamine 30%, chloroform 30%, acetate 10%.
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 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 effectively reduces environmental pollution, the especially 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.
The preparation of embodiment 1 formula (III) dye composition:
Figure BDA0000096044830000101
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 dyestuff finished product 850Kg.
The preparation of embodiment 2 formulas (IV) dye composition
Figure BDA0000096044830000111
The preparation method of formula (IV) 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 (IV);
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 dyestuff finished product 1600Kg.
The preparation of embodiment 3 formula V dye compositions:
Figure BDA0000096044830000121
The preparation method of formula V dye composition comprises the steps:
A aniline-2,5-disulfonic acid diazotization reaction
In reaction kettle, add entry, add aniline-2,5-disulfonic acid 120Kg, stirring and dissolving; Add 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 3 hours; Eliminate excessive nitrous acid with thionamic acid, get aniline-2,5-disulfonic acid diazonium liquid;
The reaction of b acid coupling
With H acid 245Kg,, make its whole dissolvings with in 30% sodium hydroxide solution and pH=6.0-7.0.Be added drop-wise to the aniline-2 that step a makes, in the 5-disulfonic acid diazonium liquid, control T=0-5 ℃, reacted 10 hours, get acid coupling liquid;
C two contracts synthesizing of thing:
In 2 tons of retort, add entry 500Kg, add Monoethanolamine MEA BASF sulfuric ester 85.6Kg, adjust T=15-40 ℃, use NaHCO 3Transfer pH=5.0-6.5, get Monoethanolamine MEA BASF sulfuric ester solution, treat a step condensation, in 5 tons of retort, add ice, water and ice milling aid; Add cyanuric chloride 165Kg then, behind the mixing, drip Monoethanolamine MEA BASF sulfuric ester solution, keep T=0-15 ℃, pH=2-5; Dropwise, reacted then 5 hours, the thing that contracts, contracting one then adds 2,4-diamino benzene sulfonic acid sodium 196Kg in the thing; Adjust T=15-40 ℃, pH=5-8, in 6 hours reaction times, chromatography detects, the two thing solution that contract;
The contract diazotization reaction of thing of d two
Two contract and add 30% hydrochloric acid soln in the thing solution to what step c made, 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 3 hours, and eliminated excessive nitrous acid with thionamic acid, the two thing diazonium liquid that contract;
E. alkaline coupling reaction
15-25 ℃ of the acid coupling liquid adjustment temperature that makes step b, 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 and kept 2 hours; The TLC plate confirms, treats aftertreatment after qualified, alkaline coupling liquid; Promptly get the dye solution of structure formula V;
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 dyestuff finished product 1156Kg.
The preparation of embodiment 4 formulas (VI) compound
Figure BDA0000096044830000131
The preparation method of formula (VI) compound comprises the steps:
A, two thing that contracts is synthetic
In 2 tons of retort, add entry 500Kg, add Monoethanolamine MEA BASF sulfuric ester 85.6Kg, adjust T=15-40 ℃, use NaHCO 3Transfer pH=5.0-6.5, get Monoethanolamine MEA BASF sulfuric ester solution, treat a step condensation, in 5 tons of retort, add ice, water and ice milling aid; Add cyanuric chloride 165Kg then, behind the mixing, drip Monoethanolamine MEA BASF sulfuric ester solution, keep T=0-15 ℃, pH=2-5; Dropwise, reacted then 5 hours, the thing that contracts, contracting one adds 2,4-diamino benzene sulfonic acid sodium 196Kg in the thing; Adjust T=15-40 ℃, pH=5-8, in 6 hours reaction times, chromatography detects, the two thing solution that contract;
The contract diazotization reaction of thing of b, two
Two contract and add 30% hydrochloric acid soln in the thing solution to what step a 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, and eliminated excessive nitrous acid with thionamic acid, the two thing diazonium liquid that contract;
C, acid coupling reaction
With H acid 245Kg, be neutralized to pH=6.0-7.0 with 30% sodium hydroxide solution, make its whole dissolvings.What be added dropwise to that step (b) makes two contracts in the thing diazonium liquid, controls T=0-5 ℃, reacted 10 hours, acid coupling liquid;
D, one contracts synthesizing of thing:
In 2 tons of retort, add entry 500Kg, add 2,5-diamino benzene sulfonic acid sodium 158.5kg adjust temperature T=0-5 ℃, adds 2,3-two bromo propionyl chloro 165kg, and 4 hours reaction times, finish, the thing solution that must one contracts,
The contract diazotization reaction of thing of e,
One contract and add 30% hydrochloric acid soln in the thing solution to what steps d made, 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, and eliminated excessive nitrous acid with thionamic acid, the thing diazonium liquid that contracts;
F. alkaline coupling reaction
15-25 ℃ of the acid coupling liquid adjustment temperature that makes step c, the thing diazonium drop that contracts that step e is made is added in the acid coupling liquid, transfers pH=5.5-7.0 with soda ash in the dropping; Drip to finish and kept 2 hours; The TLC plate confirms, treats aftertreatment after qualified, alkaline coupling liquid.Promptly get the dye solution of structural formula (VI).
G. remove insolubles: the alkaline coupling liquid that the f step is obtained joins in the solid-liquid separator and separates, and removes waste residue, collects filtrating,
H. adjust coloured light and intensity: the filtrating of g 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,
I. remove insolubles: the look liquid of h 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, get the dyestuff finished product.
The preparation of embodiment 5 formulas (VII) dye composition
Figure BDA0000096044830000151
The preparation method of formula (VII) dye composition comprises the steps:
A, aniline diazotization reaction
In 60kg aniline, add 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 3 hours, and eliminated excessive nitrous acid, get aniline diazotization solution with thionamic acid;
B, acid coupling reaction
With H acid 245Kg, be neutralized to pH=6.0-7.0 with 30% sodium hydroxide solution, make its whole dissolvings.Be added drop-wise in the aniline diazotization solution that step a makes, control T=0-5 ℃, reacted 10 hours, acid coupling liquid;
C, one contracts synthesizing of thing:
In 2 tons of retort, add entry 500Kg, add 2,5-diamino benzene sulfonic acid sodium 158.5kg adjust temperature T=0-5 ℃, adds 2, and 3-two bromo propionyl chloro 165kg reacted 4 hours, finishes, the thing solution that must one contracts,
The contract diazotization reaction of thing of d,
One contract and add 30% hydrochloric acid soln in the thing solution to what step c made, 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 3 hours, and eliminated excessive nitrous acid with thionamic acid, the thing diazonium liquid that contracts;
E. alkaline coupling reaction
15-25 ℃ of the acid coupling liquid adjustment temperature that makes step b, the thing diazonium drop that contracts that steps d is made is added in the acid coupling liquid, transfers pH=5.5-7.0 with soda ash in the dropping; Drip to finish and kept 2 hours; The TLC plate confirms, treats aftertreatment after qualified, alkaline coupling liquid.Promptly get the dye solution of structural formula (VII).
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 structural formula information of the compound of being mentioned among the present invention is:
The para-ester chemistry is by name: to (beta-hydroxyethyl sulfone sulfate) aniline, structural formula is as follows:
Figure BDA0000096044830000161
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:
Figure BDA0000096044830000163
2,3-two bromo propionyl chloros, structural formula is:
Figure BDA0000096044830000164
The structural formula of Monoethanolamine MEA BASF sulfuric ester is NH 2CH 2CH 2OSO 3H.
The application performance table of the dyestuff of embodiments of the invention 1:
Figure BDA0000096044830000165
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 (10)

1. black and active dye, it is characterized in that: these reactive dyestuffs have the general structure as shown in the formula (I):
Figure FDA0000096044790000011
In the formula (I)
R 1For-H or-SO 3M or-OCH 3
R 2For-H or-SO 3M or-SO 2C 2H 4OSO 3M or-CH 3Or-OCH 3Or
Figure FDA0000096044790000012
R 3For-H or-SO 3M or-SO 2C 2H 4OSO 3M;
R 4For-H or-SO 3M or-OH;
R 5For-H
Figure FDA0000096044790000013
Figure FDA0000096044790000014
M is-K or-Na;
And structural formula (I) does not comprise substituent R 1, R 2, R 3, R 4, R 5, M is the compound of following structure:
R 1For-H or-SO 3M or-OCH 3R 2For-H or-SO 3M or-CH 3Or-OCH 3R 3For-H or-SO 3M; R 4For-H or-SO 3M or-OH; R 5For-H; M is-K or-Na.
2. black and active dye according to claim 1 is characterized in that: M is-Na.
3. black and active dye according to claim 1 and 2 is characterized in that:
In the formula (I)
R 1For-H or-SO 3M or-OCH 3
R 2For-H or-SO 3M or-CH 3Or-OCH 3
R 3For-SO 2C 2H 4OSO 3M;
R 4For-H or-SO 3M or-OH;
R 5For
Figure FDA0000096044790000021
Figure FDA0000096044790000022
M is-Na.
4. black and active dye according to claim 1 and 2 is characterized in that:
In the formula (I)
R 1For-H or-SO 3M or-OCH 3
R 2For-SO 2C 2H 4OSO 3M or
Figure FDA0000096044790000023
Figure FDA0000096044790000024
R 3For-H or-SO 3M;
R 4For-H or-SO 3M or-OH;
R 5For
Figure FDA0000096044790000025
Figure FDA0000096044790000031
M is-Na.
5. the preparation method of claim 1 or 2 described black and active dyes is characterized in that: comprise the steps:
(a) diazotization reaction:
Any compound in the following structural formula (X-1) to (X-8) 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-4) sulfonation para-ester
(X-5) O-methoxy para-ester
(X-6) position ester between O-methoxy
Figure FDA0000096044790000043
(X-7) gram Li Xiding para-ester
Figure FDA0000096044790000044
(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 wherein 4, R 5Implication isostructure general formula (I)
(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).
6. the preparation method of black and active dye according to claim 5 is characterized in that: comprise the steps:
(a) diazotization reaction:
Any compound in the following structural formula (X-1) to (X-8) 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;
Figure FDA0000096044790000052
Figure FDA0000096044790000061
(X-4) sulfonation para-ester
Figure FDA0000096044790000062
(X-5) O-methoxy para-ester
(X-6) position ester between O-methoxy
(X-7) gram Li Xiding para-ester
Figure FDA0000096044790000065
(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;
Figure FDA0000096044790000071
R wherein 4, R 5Implication isostructure general formula (I);
(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).
7. according to the preparation method of claim 5 or 6 described black and active dyes, it is characterized in that: the structure of described structural formula (II) is any compound among (X-1), (X-2), (Y-1), (Y-2), (Y-3);
Figure FDA0000096044790000072
Figure FDA0000096044790000081
8. according to the preparation method of each described black and active dye of claim 5-7, it is characterized in that: wherein the contract preparation method of thing of (X-1) two comprises the steps: in retort, to add entry, adds para-ester again, adjusts T=15-40 ℃, uses NaHCO 3Or Na 2CO 3Transfer pH=7.0-7.5, get para-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 that makes; Keep T=0-15 ℃, pH=2-5 dropwises, and reacts then 3-5 hour; The thing that contracts, contracting one adds 2 in the thing, 4-diamino benzene sulfonic acid sodium is adjusted T=15-40 ℃; PH=4-6 reacted 2-8 hour, made (X-1) two thing that contracts, and is as follows:
Figure FDA0000096044790000091
9. according to the preparation method of each described black and active dye of claim 5-8, it is characterized in that: wherein the contract preparation method of thing of (X-2) two comprises the steps:
In retort, add entry, add the Monoethanolamine MEA BASF sulfuric ester, adjust T=15-40 ℃, use NaHCO 3Transfer pH=5.0-6.5, get Monoethanolamine MEA BASF sulfuric ester solution, treat a step condensation, in another retort, add ice, water and ice milling aid; Add cyanuric chloride then, behind the mixing, drip Monoethanolamine MEA BASF sulfuric ester solution, keep T=0-15 ℃, pH=2-5; Dropwise, reacted then 3-5 hour, the thing that contracts, contracting one then adds 2,4-diamino benzene sulfonic acid sodium in the thing; Adjust T=15-40 ℃, pH=5-8, reaction times 4-7 hour, chromatography detected, (X-2) two thing that contracts is as follows:
Figure FDA0000096044790000092
10. claim 1 or 2 described dyestuffs are used to dye cotton textiles or the painted purposes of cotton wool blending fabric.
CN2011102972343A 2011-09-29 2011-09-29 Black active dye for pure cotton or cotton and wool blended textile dyeing and preparation method thereof Pending CN102433026A (en)

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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
CN109233331A (en) * 2018-10-26 2019-01-18 天津德凯化工股份有限公司 One kind being suitable for digital ink-jet printed navy reactive dye for wool and preparation method thereof
CN109232332A (en) * 2018-10-26 2019-01-18 天津德凯化工股份有限公司 A kind of preparation method suitable for digital ink-jet printed or dyeing dyestuff intermediate
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