CN103965649A - Preparation method for azo disperse dye with stable crystal form - Google Patents
Preparation method for azo disperse dye with stable crystal form Download PDFInfo
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- CN103965649A CN103965649A CN201310045497.4A CN201310045497A CN103965649A CN 103965649 A CN103965649 A CN 103965649A CN 201310045497 A CN201310045497 A CN 201310045497A CN 103965649 A CN103965649 A CN 103965649A
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Abstract
The invention provides a preparation method for an azo disperse dye with a stable crystal form. According to the method, arylamine is used as a raw material, and diazotization, coupling, crystal transformation, press filtration and washing are successively carried out so as to obtain the dye; an ammonium salt is added during coupling and/or crystal transformation, the addition amount of the ammonium salt is such controlled that the concentration of the ammonium salt in a reaction system of coupling and/or crystal transformation is allowed to be no more than 25%, and the ammonium salt is one or more selected from the group consisting of ammonium sulfate or ammonium chloride, a neutralized liquid prepared by neutralizing acidic dye waste water with ammonia and decoloring the neutralized acidic dye waste water with active carbon, and mother liquor prepared by neutralizing the acidic dye waste water with ammonia, decoloring the neutralized acidic dye waste water with active carbon and carrying out concentration, crystallization and separation. The invention mainly has the following beneficial effects: with a dye filter cake prepared by using the method, sand milling time is obviously shortened during commercial processing; the finished dye has a higher melting point, better storage stability and improved purity, and colored light of the finished dye is brilliant and not dark compared with a standard product.
Description
(1) technical field
The present invention relates to a kind of method of preparing stable crystal form azo dispersion dyes.
(2) background technology
In disperse dyeing process, although a lot of dyestuff can obtain the product that every fastness ability is good, the high temperature dispersibility that causes because of its crystal formation is bad to be caused dyeing inhomogeneous, exists the unusual phenomenoies such as color spot and color dot to occupy significant proportion.Therefore, the relation of research dyestuff crystal formation and dyeing behavior, contributes to improve application performance, improves commercial dye inner quality, obtains better effect.But the means of existing improvement dyestuff crystal formation are more limited, be mainly after completing by coupling, the mode that turns brilliant that heats up is carried out, and the method report that rarely has other to improve dyestuff crystal formation.
(3) summary of the invention
The object of the invention is to provide a kind of method of stable crystal form azo dispersion dyes.
The technical solution used in the present invention is:
A kind of method of preparing stable crystal form azo dispersion dyes, described method be with arylamine raw material successively through conventional diazotization, coupling, turn brilliant, filter-press water-washing and obtain dye product, the present invention adds ammonium salt in coupling and/or in turning brilliant operation, the add-on of ammonium salt is that in control coupling and/or the reaction system that turns brilliant operation, ammonium salt concentration is no more than 25%(w/w, ammonium salt/(ammonium salt+water)); Described ammonium salt derives from one or more in following raw materials according: ammonium sulfate or ammonium chloride (salt or solution form), neutralizer for Acid Dye Wastewater after ammonia neutralization activated carbon decolorizing, Acid Dye Wastewater is the mother liquor by condensing crystal separation with ammonia neutralization activated carbon decolorizing.Wherein, ammonium sulfate is applicable to carry out diazotizing technique with sulfuric acid, Sodium Nitrite or nitrosyl sulfuric acid, and ammonium chloride is applicable to carry out diazotizing technique with hydrochloric acid, Sodium Nitrite.
Described Acid Dye Wastewater refers to isolated acid waste water in azo disperse dye production process, specifically can be the sulfur acid of press filtration separation or the acid mother liquid water of hydrochloric acid and/or the washing water of pH<3 after coupling.Wastewater source: arylamine diazo component adds under the existence that nitrosyl sulfuric acid or hydrochloric acid adds Sodium Nitrite and carries out diazotization in a known manner at sulfuric acid, again with coupling component coupling in a known manner, through turning brilliant, filter-press water-washing, isolate acid waste water standby, filter cake is for follow-up commercialization processing.
The concrete preparation method of neutralizer after described decolouring is as follows: by isolated acid waste water in azo disperse dye production process, all or part of with ammonia, to be neutralized to pH value be 3 ~ 8, filter, remove the impurity of separating out, obtain neutralizer, neutralizer activated carbon decolorizing, filter and remove active breeze, obtain the solution of liquid containing ammonium sulfate or ammonium chloride, be the neutralizer after described decolouring.
Ammonium salt of the present invention can be chosen in following single or multiple operation sequence and add: in the end water before coupled reaction, in coupled reaction process, coupled reaction heats up and to turn before crystalline substance, turn in crystalline substance and turn after crystalline substance.
Preferably, the diazo component of preparing described dispersed dye is one of following: p-Nitroaniline, 2,4-dinitrobenzene-6-chloroaniline, 2,4-dinitrobenzene-6-bromaniline, the chloro-4-N-methyl-p-nitroaniline of 2-, 2,6-Dichloro-4-nitroaniline, 2, the bromo-4-N-methyl-p-nitroaniline of 6-bis-, 2 cyano 4 nitro aniline, 2-cyano group-4,6-dinitraniline, 2,6-dicyano-4-N-methyl-p-nitroaniline, 2-amino-5,6(6,7)-dichlorobenzothiazole, 2-amino-6-nitrobenzothiazole, 3-amino-5-nitro benzisothiazole etc.
Preferably, the coupling component of preparing described dispersed dye is one of following: 2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-diacetyl oxy ethyl aniline, 2-oxyethyl group-5-acetylaminohydroxyphenylarsonic acid N, N-diacetyl oxy ethyl aniline, 2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-diallyl aniline, 2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-Diethyl Aniline, 2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-dimethoxy phosphinylidyne ethylaniline, 2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-dimethoxy phosphinylidyne monomethylaniline, 3-acetylaminohydroxyphenylarsonic acid N, N-Diethyl Aniline, N-cyanoethyl-Phenhenzamine, N-cyanoethyl-Phenhenzamine, N-ethyl-N-cyanoethyl aniline etc.
Beneficial effect of the present invention is mainly reflected in: the dyestuff filter cake that adopts the method for the invention to obtain, in the commercialization course of processing, the sand milling time obviously shortens.Finished product dyestuff fusing point is higher, and storage stability is better, and dyestuffs purity improves, and coloured light is compared bright-coloured not withering secretly with standard substance.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1:C.I. 63 DISPERSE Violet 63 93(is V93)
(1) diazotization
By 667kg40%(w/w) nitrosyl sulfuric acid and 500kg98%(w/w) vitriol oil puts into diazonium pot and stirs, chuck leads to cooling water temperature to 10 ~ 20 ℃; In 6 ~ 8 hours, evenly add 435kg6-chloro-2,4-dinitraniline, controls 10 ~ 20 ℃ of stirring reactions of temperature 2 ~ 3 hours, and diazo liquid splashes into be clarified diazotization in frozen water and complete.
(2) coupling, turn crystalline substance, press filtration, washing (adding ammonium sulfate in the end water before coupled reaction)
In coupling pot, add 4000L fresh water as end water, add 620 grams of ammonium sulfate, the m-acetylaminohydroxyphenylarsonic acid N of 416kg, N-Diethyl Aniline, add auxiliary agent urea 2kg, peregal 5kg,, making beating 30 ~ 45min, adds 3000kg ice and is cooled to 0 ℃ of left and right, add defoamer and eliminate foam, in 2 ~ 3 hours, drip the diazo liquid that upper step reaction obtains, control 0 ℃ of left and right of temperature, continue insulated and stirred 2 ~ 3 hours, slowly be warmed up to 40 ~ 45 ℃, be incubated 1 ~ 1.5 hour, press filtration, isolates acid mother liquid, with 40 ~ 60 ℃ of hot washes, to neutral, obtain C.I. 63 ,DIS,PER,SE ,Vio,let, 63 93 filter cakes.
Embodiment 2:C.I. EX-SF DISPERSE BLUE EX-SF 300 291:1(is B291:1)
(1) diazotization
The nitrosyl sulfuric acid of 647kg40% and the 420kg98% vitriol oil are put into diazonium pot to stir, stir, be cooled to 10 ~ 20 ℃, in 6 ~ 8 hours, evenly add 524kg6-bromo-2,4-dinitraniline, control 10 ~ 20 ℃ of temperature and continue stirring reaction 2 ~ 3 hours, detection reaction terminal, standby after diazotization completes.
(2) coupling, turn crystalline substance, press filtration, washing (destainer that adds liquid containing ammonium sulfate in the end water before coupled reaction)
Getting the vitriolated acid mother liquid waste water of collecting in B291:1 DYE PRODUCTION process neutralizes with liquefied ammonia, filter and add the destainer 9500L(ammonium sulfate content 7.6% of decolorization and impurity removal by active carbon gained) add and in coupling pot, do end water, add 520kg coupling component diallyl reduzate (2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-diallyl aniline), add again auxiliary agent urea 3kg, fast penetrant T 15kg, making beating 30 ~ 45min, add 2000kg ice and open chilled brine simultaneously, make material be cooled to 0 ℃ of left and right, drop into defoamer defoamer, in 2 ~ 3 hours, drip the diazo liquid that upper step reaction obtains, control 0 ℃ of left and right of temperature, continue insulated and stirred 2 ~ 3 hours, slowly be warmed up to ~ 40 ℃, be incubated 1 ~ 1.5 hour, press filtration, extremely neutral with the hot wash of 40 ℃ of left and right, make C.I. EX-SF DISPERSE BLUE EX-SF 300 291:1 filter cake.
Embodiment 3:C.I. Disperse Blue-79 (being B79)
(1) diazotization
The nitrosyl sulfuric acid of 810kg40% and the 500kg98% vitriol oil are put into diazonium pot to stir, stir, be cooled to 10 ~ 20 ℃, in 6 ~ 8 hours, evenly add 655kg6-bromo-2,4-dinitraniline, control 10 ~ 20 ℃ of temperature and continue stirring reaction 2 ~ 3 hours, detection reaction emphasis, has reacted rear standby.
(2) coupling, turn crystalline substance, press filtration, washing (after coupled reaction, heat up and turn the destainer that adds liquid containing ammonium sulfate before crystalline substance)
Get 6300kg fresh water and add coupling pot as end water, add the dark blue esterifying liquid of 880kg (2-methoxyl group-5 acetylaminohydroxyphenylarsonic acid N, N-diacetyl oxy ethyl aniline), add again auxiliary agent urea 2kg, peregal 15kg, pull an oar 0.5 ~ 1 hour, add 5000kg ice, material is cooled to 0 ℃ of left and right, drop into defoamer defoamer, start from dripping in 2.5 ~ 4 hours step (1) gained diazo liquid, whole process is strictly controlled 0 ℃ of left and right of temperature, adding rear insulation continues to stir 2 ~ 3 hours, adding 2000kg ammonium sulfate concentrations is in 9.46% dyestuff acid waste water and destainer, slowly be warmed up to 40 ℃, continue insulation 1 ~ 2 hour, press filtration, extremely neutral with hot wash, obtain C.I. Disperse Blue-79 filter cake.
Embodiment 4:C.I. DISPERSE ORANGE 30 200 288(is O288)
(1) diazotization
The hydrochloric acid of 417kg water, 276kg p-Nitroaniline, 973kg30% is added to diazonium pot, pull an oar 8 ~ 10 hours, on the rocks being cooled to below 0 ℃, under liquid level, add fast the sodium nitrite solution of 403kg36%, control 0 ℃ of left and right stirring reaction of temperature 3 ~ 4 hours, with potassium iodide starch test paper, detect doazo reaction emphasis, diazo liquid is standby.
(2) coupling, turn crystalline substance, press filtration, washing (destainer that adds containing ammonium chloride in the end water before coupled reaction)
Hydrochloric acid mother liquid and the washes of getting front a collection of coupled reaction separation mix, with liquefied ammonia neutralization, decolouring, the destainer of gained containing ammonium chloride 8.7% is got 1550L, add coupling pot, add 1160kg ice, then the diazo liquid that is reacted to terminal is joined in coupling pot and diluted, while having diluted, temperature is controlled at below 5 ℃.After having diluted, stir and add auxiliary agent thionamic acid 2.5kg, TX-105kg, fast penetrant T 8kg, stir, control temperature, slowly evenly add 467kg N-cyanoethyl-Phenhenzamine; Holding temperature, 10 ~ 15 ℃ of reactions 2 ~ 3 hours, then adds 1900kg water, and heating, is warmed up to 40 ℃ by material, and then insulation reaction is 3 ~ 6 hours, carries out press filtration washing to neutral, obtains DISPERSE ORANGE 30 200 288 filter cakes.
To make the filter cake of coupling water production with fresh water, compare, the dyestuff filter cake obtaining is through sand milling, stdn, adopt again high-temperature pressure dyeing technique to dye to polyester piece good, and judge its coloured light and intensity by GB/T2394, and result is as following table, and data show in coupling operation and/or turn brilliant operation to add ammonium salt, the sand milling time obviously shortens, fusing point increases, and purity promotes, and coloured light is bright-coloured not to wither secretly.
Claims (3)
1. a method of preparing stable crystal form azo dispersion dyes, described method be with arylamine raw material successively through diazotization, coupling, turn brilliant, filter-press water-washing and obtain dye product, it is characterized in that: in coupling and/or in turning brilliant operation, add ammonium salt, the add-on of ammonium salt is that in control coupling and/or the reaction system that turns brilliant operation, ammonium salt concentration is no more than 25%; Described ammonium salt derives from one or more in following raw materials according: ammonium sulfate or ammonium chloride, and the neutralizer for Acid Dye Wastewater after ammonia neutralization activated carbon decolorizing, Acid Dye Wastewater is the mother liquor by condensing crystal separation with ammonia neutralization activated carbon decolorizing.
2. the method for claim 1, the diazo component that it is characterized in that preparing described dispersed dye is one of following: p-Nitroaniline, 2,4-dinitrobenzene-6-chloroaniline, 2,4-dinitrobenzene-6-bromaniline, the chloro-4-N-methyl-p-nitroaniline of 2-, 2,6-Dichloro-4-nitroaniline, 2, the bromo-4-N-methyl-p-nitroaniline of 6-bis-, 2 cyano 4 nitro aniline, 2-cyano group-4,6-dinitraniline, 2,6-dicyano-4-N-methyl-p-nitroaniline, 2-amino-5,6(6,7)-dichlorobenzothiazole, 2-amino-6-nitrobenzothiazole, 3-amino-5-nitro benzisothiazole.
3. the method for claim 1, the coupling component that it is characterized in that preparing described dispersed dye is one of following: 2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-diacetyl oxy ethyl aniline, 2-oxyethyl group-5-acetylaminohydroxyphenylarsonic acid N, N-diacetyl oxy ethyl aniline, 2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-diallyl aniline, 2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-Diethyl Aniline, 2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-dimethoxy phosphinylidyne ethylaniline, 2-methoxyl group-5-acetylaminohydroxyphenylarsonic acid N, N-dimethoxy phosphinylidyne monomethylaniline, 3-acetylaminohydroxyphenylarsonic acid N, N-Diethyl Aniline, N-cyanoethyl-Phenhenzamine, N-cyanoethyl-Phenhenzamine, N-ethyl-N-cyanoethyl aniline.
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Cited By (6)
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| CN105440737A (en) * | 2014-08-29 | 2016-03-30 | 浙江迪邦化工有限公司 | Preparation method of energy-efficient and environmentally-friendly disperse dye |
| CN105440727A (en) * | 2014-08-29 | 2016-03-30 | 浙江迪邦化工有限公司 | Preparation method of ester group-containing azo disperse dye |
| CN105623299A (en) * | 2015-11-19 | 2016-06-01 | 浙江闰土研究院有限公司 | Compound novel crystal form as well as preparation method and purpose thereof |
| CN106398272A (en) * | 2015-08-03 | 2017-02-15 | 浙江永合化工有限公司 | One-pot-method synthesis process for disperse orange 288 |
| CN106687532A (en) * | 2014-09-30 | 2017-05-17 | 富士胶片株式会社 | Method for producing azo dye, organic amine salt, method for producing organic amine salt, azo compound and method for producing azo compound |
| CN113372734A (en) * | 2021-05-21 | 2021-09-10 | 浙江亿得新材料股份有限公司 | Cycle-based orange dye synthesis method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440737A (en) * | 2014-08-29 | 2016-03-30 | 浙江迪邦化工有限公司 | Preparation method of energy-efficient and environmentally-friendly disperse dye |
| CN105440727A (en) * | 2014-08-29 | 2016-03-30 | 浙江迪邦化工有限公司 | Preparation method of ester group-containing azo disperse dye |
| CN105440727B (en) * | 2014-08-29 | 2017-09-22 | 浙江迪邦化工有限公司 | A kind of preparation method with ester group azo dispersion dyes |
| CN106687532A (en) * | 2014-09-30 | 2017-05-17 | 富士胶片株式会社 | Method for producing azo dye, organic amine salt, method for producing organic amine salt, azo compound and method for producing azo compound |
| CN106687532B (en) * | 2014-09-30 | 2019-10-25 | 富士胶片株式会社 | The manufacturing method of the manufacturing method of azopigment, the manufacturing method of organic amine salt and organic amine salt and azo-compound and azo-compound |
| CN106398272A (en) * | 2015-08-03 | 2017-02-15 | 浙江永合化工有限公司 | One-pot-method synthesis process for disperse orange 288 |
| CN105623299A (en) * | 2015-11-19 | 2016-06-01 | 浙江闰土研究院有限公司 | Compound novel crystal form as well as preparation method and purpose thereof |
| CN113372734A (en) * | 2021-05-21 | 2021-09-10 | 浙江亿得新材料股份有限公司 | Cycle-based orange dye synthesis method |
| CN113372734B (en) * | 2021-05-21 | 2023-02-17 | 浙江亿得新材料股份有限公司 | Cycle-based orange dye synthesis method |
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