CN102337044A - Reactive dye and preparation method thereof - Google Patents
Reactive dye and preparation method thereof Download PDFInfo
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- CN102337044A CN102337044A CN2011102998875A CN201110299887A CN102337044A CN 102337044 A CN102337044 A CN 102337044A CN 2011102998875 A CN2011102998875 A CN 2011102998875A CN 201110299887 A CN201110299887 A CN 201110299887A CN 102337044 A CN102337044 A CN 102337044A
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Abstract
The invention relates to a reactive dye and a preparation method thereof. The structural general formula of the reactive dye is shown in the specification. M is -H or alkali metal, preferably, -Na. The reactive dye has good water solubility, high affinity under the dyeing condition, wide printing and dying technological applicability, low environmental pollution, gorgeous color light, excellent operational performances and no free heavy metal.
Description
Technical field
The present invention relates to a kind of dyestuff, especially a kind of reactive dyestuffs and preparation method thereof.
Background technology
Present main on the market dyestuff is main with matching stain, dispersed dye, mordant dyes and metallized dye still; It is not good enough that the dyestuff of above type dyes the material fastness; Coloured light is not gorgeous, and the dyeing clean absorption rate is low, and degree of fixation is low; Big for environment pollution, particularly the metallized dye free heavy metal that possibly occur all has harm to human body with to environment.Along with the progress of society, people's environmental consciousness is more and more stronger, and the environmental friendliness type dye becomes present development trend.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; A good water solubility is provided, last dying under the condition high-affinity is arranged, the dyeing and printing process suitability is wide; Environmental pollution is little, coloured light is gorgeous, each item use properties excellent, does not have azo-type blue active dye of free heavy metal and preparation method thereof.
For solving the problems of the technologies described above, the scheme that the present invention takes is: a kind of blue active dye has the general structure with following formula (I):
Formula (I) M is-H or basic metal that preferably, M is-Na.
Preferably, this blue active dye has the structural formula of formula (II):
The present invention also provides the preparation method of above-mentioned formula (II) blue active dye, comprises the steps:
A), para-ester (or position ester) diazotization:
Xiang Shuizhong adds para-ester (or position ester), adds ice and hydrochloric acid soln again, adds sodium nitrite solution, carries out diazotization reaction, and reaction finishes and removes remaining nitrous acid with thionamic acid, gets diazotization solution, and is subsequent use;
B), H acid dissolving:
Xiang Shuizhong adds H acid, stirs, and transfers pH=6.5-7.5 with 30%NaOH solution, obtains the H acid solution after the dissolving fully, and is subsequent use;
C), a step coupling:
With b) the H acid solution of step preparation joins in the diazotization solution of a) step preparation, stirring reaction 3-4 hour, a step coupling solution, subsequent use;
D), 4-beta-hydroxyethyl sulfonyl imines-naphthalidine diazotization
Xiang Shuizhong adding 4-beta-hydroxyethyl sulfonyl imines-naphthalidine adds ice and hydrochloric acid soln again, adds sodium nitrite solution, carries out diazotization reaction, and reaction finishes and removes remaining nitrous acid with thionamic acid, gets diazotization liquid, and is subsequent use;
E), two step couplings:
With d) the diazotization liquid of step preparation joins in the step coupling solution of step c) preparation, stirs, and uses Na
2CO
3Make acid binding agent, transfer pH=7～8, be warming up to 15-30 ℃, react 3-6 hour, reaction finishes to such an extent that two go on foot coupling solutions, and is subsequent use;
F), de-ester reaction:
With e) two step coupling solutions of step gained maintain the temperature between 0-50 ℃, transfer pH=8～11 with 30%NaOH solution, carry out de-ester reaction, react 4-8 hour, must de-ester reaction liquid, promptly be formula (II) blue active dye solution.
Preferably, the preparation method of this blue active dye also comprises the steps:
G), saltout:
To f) add NaCl in the de-ester reaction liquid of step gained, treat that dyestuff separates out filtration, get filter cake and get dyestuff,
H), drying:
With g) collect the filter cake obtain and dry, pulverize, the dyestuff finished product.
Among the above-mentioned preparation method, 4-beta-hydroxyethyl sulfonyl imines-naphthalidine by naphthalidine-4-sulfonic acid via acetylize, chlorosulphonation, condensation, hydrolysis, saltouing obtains.Concrete working method is following:
D1), acetylize:
With 55.75g naphthalidine-4-sulfonic acid dissolving, be warming up to 40 ℃, (below the liquid level) drips the 40.8g diacetyl oxide under the liquid, is warming up to 60-65 ℃ in the process, behind the reaction 15-20min, is cooled to 20-30 ℃, transfers pH=7-7.5, reacts 3-6 hour; Solution spray is dry, obtain 1-acetylaminohydroxyphenylarsonic acid 4-naphthene sulfonic acid dry product.
D2), chlorosulphonation:
In the 1000ml four-hole bottle, add chlorsulfonic acid 116.5g, with d1) the 1-acetylaminohydroxyphenylarsonic acid 4-naphthene sulfonic acid dry product of step preparation, join in the chlorsulfonic acid; Stir, be warming up to 120 ℃, reacted 4 hours; Be cooled to 60 ℃ and add the 68.4g sulfur oxychloride, reacted 2 hours, be warming up to 90-95 ℃ of insulation 0.5 hour; Be warming up to 105-110 ℃ of insulation 0.5 hour again, be cooled to below 40 ℃, get the chlorosulphonation feed liquid.In the 3000ml beaker, add entry 200ml, trash ice 500g stirs and adds the chlorosulphonation feed liquid down, adds trash ice in good time and keeps system temperature to be lower than 0 ℃, gets solidliquid mixture.This solidliquid mixture is filtered, and it is subsequent use to get filter cake.
D3), condensation:
In the 1000ml beaker, add entry 200ml, Monoethanolamine MEA BASF 13.0g stirs and dissolves to complete, Monoethanolamine MEA BASF solution, with d2) filter cake of preparation joins in the Monoethanolamine MEA BASF solution, is warming up to 40-50 ℃, keeps pH=10-11, react 4-8 hour, gets condensated liquid.
D4), hydrolysis:
At d3) in the condensated liquid of step preparation, add the NaOH solid of condensated liquid volume 3～4%, be warming up to 90-100 ℃ of reaction 3-6 hour, hydrolyzed solution.
D5), saltout
At d4) hydrolyzed solution of step preparation adds Repone K, and 4-beta-hydroxyethyl sulfonyl imines-naphthalidine is separated out, treat that 4-beta-hydroxyethyl sulfonyl imines-naphthalidine is separated out after, filter, collect filter cake, detection level is subsequent use.
The present invention also provides said structure formula (I) compound to be used for the purposes of cotton textiles or dyeing nylon.
Among the preparation method of above-claimed cpd and compound,
Para-ester is claimed again (beta-sulfuric ester ethyl sulfonyl) aniline, the vinyl sulfone(Remzaol sulfuric ester, and 4-sulfovinic acid sulfuryl aniline, right-beta-hydroxy second sulfone aniline sulfuric ester or right-beta-hydroxy second sulfone aniline sulfuric ester, its structural formula is following:
Between the position ester be between the abbreviation of (beta-sulfuric ester ethyl sulfonyl base) aniline, its structural formula is following:
H acid is 1-amino-8-naphthol-3, the abbreviation of 6-disulfonate sodium, and its structural formula is following:
The structural formula of 4-beta-hydroxyethyl sulfonyl imines-naphthalidine is:
The structural formula of Monoethanolamine MEA BASF is NH
2CH
2CH
2OH.
The beneficial effect that the present invention had:
Reactive dyestuffs good water solubility of the present invention has high-affinity last dying under the condition, and the dyeing and printing process suitability is wide, and environmental pollution is little, coloured light is gorgeous, each item use properties excellent and do not have free heavy metal.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but does not limit protection scope of the present invention.
Embodiment 1
A kind of azo-type blue active dye has the structural formula of formula (III),
The preparation method of this blue active dye comprises the steps:
A), para-ester diazotization:
In the 1000ml beaker, add 200ml water and then the para-ester 28.1g of 100% amount is added, stirred 15 minutes.Again 24.3 grams, 30% hydrochloric acid soln is added.Directly with ice adjustment solution temperature less than 0 ℃, under reaction soln guarantees that the pH value is less than 2 condition, 30% sodium nitrite solution of 23.5g is added fast.0～5 ℃ of holding temperature was reacted 2 hours, remained in the reaction process to be blue after congo-red test paper soaks into, and was blue after starch KI test paper soaks into.Reaction finishes and removes remaining nitrous acid with thionamic acid, gets diazotization solution, and is subsequent use.
B), H acid dissolving:
In the 1000ml beaker, add entry, add the H acid 34.2g of 100% amount, stir, transfer pH=6.5-7.5 with 30%NaOH solution, dissolving obtains the H acid solution fully, and is subsequent use.
C), a step coupling:
With b) the H acid solution of step preparation joins in the diazotization solution of a) step preparation, stirring reaction 4 hours, temperature 7-10 ℃, a step coupling solution, subsequent use.
D), 4-beta-hydroxyethyl sulfonyl imines-naphthalidine diazotization
In the 1000ml beaker, add 200ml water and then the 4-beta-hydroxyethyl sulfonyl imines-naphthalidine 34.6g of 100% amount is added, stirred 15 minutes.Again 24.3g 30% hydrochloric acid soln is added.Directly adjust solution temperature less than 0 ℃, under reaction soln guarantees that the pH value is less than 2 condition, 23.5g 30% sodium nitrite solution is added fast with ice.0～5 ℃ of holding temperature was reacted 2 hours, remained in the reaction process to be blue after congo-red test paper soaks into, and was blue after starch KI test paper soaks into.Reaction finishes and removes remaining nitrous acid with thionamic acid, gets diazotization liquid, and is subsequent use.
E), two step couplings:
With d) step prepares in the step coupling solution that diazotization liquid joins step c) preparation, stirs, and uses Na
2CO
3Make acid binding agent, transfer pH=7～8,25 ℃ of temperature reacts 4 hours, and reaction finishes to such an extent that two go on foot coupling solutions, and is subsequent use.
F), de-ester reaction:
With e) two step coupling solutions of step gained are warming up between 40-50 ℃, transfer pH=9～9.5 with 30%NaOH solution, carry out de-ester reaction, react 4 hours, must de-ester reaction liquid, promptly be formula (III) azo-type blue active dye solution.
G), saltout:
To f) add NaCl in the de-ester reaction liquid of gained and saltout, wherein sodium-chlor is 0.05g: 1mL with the ratio of de-ester reaction liquid, treats that dyestuff separates out filtration, gets filter cake and gets dyestuff
H), drying:
With g) collect the dyestuff filter cake obtain and dry, pulverize, dyestuff finished product 90g.
Among the above-mentioned preparation method, 4-beta-hydroxyethyl sulfonyl imines-naphthalidine by naphthalidine-4-sulfonic acid via acetylize, chlorosulphonation, condensation, hydrolysis, saltouing obtains.Concrete working method is following:
D1), acetylize:
With 55.75g naphthalidine-4-sulfonic acid dissolving, be warming up to 40 ℃, (below the liquid level) drips the 40.8g diacetyl oxide under the liquid, is warming up to 60-65 ℃ in the process, behind the reaction 15-20min, is cooled to 20-30 ℃, transfers pH=7-7.5, reacts 5 hours; Solution spray is dry, obtain 1-acetylaminohydroxyphenylarsonic acid 4-naphthene sulfonic acid dry product.
D2), chlorosulphonation:
In the 1000ml four-hole bottle, add chlorsulfonic acid 116.5g with d1) the 1-acetylaminohydroxyphenylarsonic acid 4-naphthene sulfonic acid dry product of step preparation, join in the chlorsulfonic acid, stir; Be warming up to 120 ℃, reacted 4 hours, be cooled to 60 ℃ and add the 68.4g sulfur oxychloride; Reacted 2 hours, and be warming up to 90-95 ℃ of insulation 0.5 hour, be warming up to 105-110 ℃ of insulation 0.5 hour again; Be cooled to below 40 ℃, get the chlorosulphonation feed liquid.In the 3000ml beaker, add entry 200ml, trash ice 500g stirs and adds the chlorosulphonation feed liquid down, adds trash ice in good time and keeps system temperature to be lower than 0 ℃, gets solidliquid mixture.This solidliquid mixture is filtered, and it is subsequent use to get filter cake.
D3), condensation:
In the 1000ml beaker, add entry 200ml, Monoethanolamine MEA BASF 13.0g stirs and dissolves to complete; Monoethanolamine MEA BASF solution, with d2) preparation filter cake, join in the Monoethanolamine MEA BASF solution; Be warming up to 40-50 ℃, keep pH=10-11, reacted 4-8 hour; Detecting with thin-layer chromatography, with steps d 2) content of product be terminal point less than 0.03, must condensated liquid.
D4), hydrolysis:
At d3) in the condensated liquid of step preparation, add the NaOH solid of condensated liquid volume 3～4%, be warming up to 90-100 ℃ of reaction 4 hours, hydrolyzed solution.
D5), saltout
At d4) hydrolyzed solution of step preparation adds the Repone K of its volume 10% amount, and 4-beta-hydroxyethyl sulfonyl imines-naphthalidine is separated out, treat that 4-beta-hydroxyethyl sulfonyl imines-naphthalidine is separated out after, filter, collect filter cake, detection level is subsequent use.
Table one: the blue performance of nylon active, quality index
Table two: performance index contrast
Embodiment 2
The position ester will obtain having the blue active dye as shown in the formula (IV) structure between para-ester in embodiment 1 preparing method's a) step is changed to
Compound of the present invention and preparation method thereof 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 (5)
1. blue active dye, it is characterized in that: this blue active dye has the general structure with following formula (I):
M is-H or basic metal.
2. blue active dye according to claim 1 is characterized in that: M is-Na.
3. blue active dye according to claim 1 and 2 is characterized in that: this blue active dye has the structural formula of formula (II):
4. the preparation method of each described blue active dye of claim 1-3 is characterized in that: comprise the steps:
A), para-ester (or position ester) diazotization:
Xiang Shuizhong adds para-ester (or position ester), adds ice and hydrochloric acid soln again, adds sodium nitrite solution, carries out diazotization reaction, and reaction finishes and removes remaining nitrous acid with thionamic acid, gets diazotization solution, and is subsequent use;
B), H acid dissolving:
Xiang Shuizhong adds H acid, stirs, and transfers pH=6.5-7.5 with 30%NaOH solution, obtains the H acid solution after the dissolving fully, and is subsequent use;
C), a step coupling:
With b) the H acid solution of step preparation joins in the diazotization solution of a) step preparation, stirring reaction 3-4 hour, a step coupling solution, subsequent use;
D), 4-beta-hydroxyethyl sulfonyl imines-naphthalidine diazotization
Adding 4-beta-hydroxyethyl sulfonyl imines-naphthalidine adds ice and hydrochloric acid soln again in end water, adds sodium nitrite solution, carries out diazotization reaction, and reaction finishes and removes remaining nitrous acid with thionamic acid, gets diazotization liquid, and is subsequent use;
E), two step couplings:
With d) the diazotization liquid of step preparation joins in the step coupling solution of step c) preparation, stirs, and uses Na
2CO
3Make acid binding agent, transfer pH=7～8, be warming up to 15-30 ℃, react 3-6 hour, reaction finishes to such an extent that two go on foot coupling solutions, and is subsequent use;
F), de-ester reaction:
With e) two step coupling solutions of step gained maintain the temperature between 0-50 ℃, transfer pH=8～11 with 30%NaOH solution, carry out de-ester reaction, react 4-8 hour, must de-ester reaction liquid, promptly be blue active dye solution.
Preferably, the preparation method of this blue active dye also comprises the steps:
G), saltout:
To f) add NaCl in the de-ester reaction liquid of step gained, treat that dyestuff separates out filtration, get filter cake and get dyestuff,
H), drying:
With g) collect the filter cake obtain and dry, pulverize, the dyestuff finished product.
5. the described blue active dye of claim 1 is used for the purposes of cotton textiles or dyeing nylon.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110299887.5A CN102337044B (en) | 2011-09-28 | 2011-09-28 | A kind of reactive dyestuffs and preparation method thereof |
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|---|---|---|---|
| CN201110299887.5A CN102337044B (en) | 2011-09-28 | 2011-09-28 | A kind of reactive dyestuffs and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327544A (en) * | 2014-10-13 | 2015-02-04 | 天津德凯化工股份有限公司 | Navy blue reactive dye and its preparation method |
| CN106349746A (en) * | 2016-08-24 | 2017-01-25 | 天津德凯化工股份有限公司 | Red reactive dye suitable for nylon dyeing and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59115360A (en) * | 1982-12-22 | 1984-07-03 | Sumitomo Chem Co Ltd | Disazo compound and method for dyeing fiber by using the same |
| US4530996A (en) * | 1981-06-15 | 1985-07-23 | Sumitomo Chemical Company, Limited | Bisazo blue-black dye having vinylsulfone type fiber-reactive group |
| CN101283054A (en) * | 2005-10-05 | 2008-10-08 | 德意志戴斯达纺织品及染料两合公司 | Azo reactive dyes and mixtures of fiber-reactive azo dyes, their preparation and their use |
-
2011
- 2011-09-28 CN CN201110299887.5A patent/CN102337044B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4530996A (en) * | 1981-06-15 | 1985-07-23 | Sumitomo Chemical Company, Limited | Bisazo blue-black dye having vinylsulfone type fiber-reactive group |
| JPS59115360A (en) * | 1982-12-22 | 1984-07-03 | Sumitomo Chem Co Ltd | Disazo compound and method for dyeing fiber by using the same |
| CN101283054A (en) * | 2005-10-05 | 2008-10-08 | 德意志戴斯达纺织品及染料两合公司 | Azo reactive dyes and mixtures of fiber-reactive azo dyes, their preparation and their use |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327544A (en) * | 2014-10-13 | 2015-02-04 | 天津德凯化工股份有限公司 | Navy blue reactive dye and its preparation method |
| CN106349746A (en) * | 2016-08-24 | 2017-01-25 | 天津德凯化工股份有限公司 | Red reactive dye suitable for nylon dyeing and preparation method thereof |
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|---|---|
| CN102337044B (en) | 2015-10-21 |
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