CN102337044B - A kind of reactive dyestuffs and preparation method thereof - Google Patents
A kind of reactive dyestuffs and preparation method thereof Download PDFInfo
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- CN102337044B CN102337044B CN201110299887.5A CN201110299887A CN102337044B CN 102337044 B CN102337044 B CN 102337044B CN 201110299887 A CN201110299887 A CN 201110299887A CN 102337044 B CN102337044 B CN 102337044B
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Abstract
The present invention relates to a kind of reactive dyestuffs and preparation method thereof, these reactive dyestuffs have the general structure with following formula:
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 dyestuff main is on the market still based on matching stain, dispersed dye, mordant dyes and metallized dye, it is not good enough that the dyestuff of above type contaminates material fastness, coloured light is not gorgeous, dyeing clean absorption rate is low, degree of fixation is low, big for environment pollution, the free heavy metal that particularly metallized dye may occur has harm to human body with to environment.Along with the progress of society, the environmental consciousness of people is more and more stronger, and environmental friendliness type dye becomes current development trend.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, there is provided a good water solubility, under upper dye condition, have high-affinity, dyeing and printing process suitability is wide, environmental pollution is little, coloured light is gorgeous, every use properties excellent, azo blue active dye of the free heavy metal of nothing 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 of following formula I:
Formula I M is-H or basic metal, and preferably, M is-Na.
Preferably, this blue active dye has the structural formula of formula II:
Present invention also offers the preparation method of above-mentioned formula II blue active dye, comprise the steps:
A), para-ester (or position ester) diazotization:
Xiang Shuizhong adds para-ester (or position ester), then adds ice and hydrochloric acid soln, adds sodium nitrite solution, carries out diazotization reaction, react complete thionamic acid and remove remaining nitrous acid, obtain diazo solution, for subsequent use;
B), H acid dissolve:
Xiang Shuizhong adds H acid, stirs, and adjusts pH=6.5-7.5 with 30%NaOH solution, obtains H acid solution after dissolving completely, for subsequent use;
C), a step coupling:
Joined by the H acid solution that b) prepared by step in diazo solution prepared by a) step, stirring reaction 3-4 hour, obtains a step coupling solution, for subsequent use;
D), the amino sulfuryl-naphthalidine diazotization of 4-beta-hydroxyethyl
Xiang Shuizhong adds the amino sulfuryl-naphthalidine of 4-beta-hydroxyethyl, then adds ice and hydrochloric acid soln, adds sodium nitrite solution, carries out diazotization reaction, react complete thionamic acid and remove remaining nitrous acid, obtain diazotization liquid, for subsequent use;
E), two step couplings:
The diazotization liquid that d) prepared by step is joined step c) in the step coupling solution prepared, stir, use Na
2cO
3make acid binding agent, adjust pH=7 ~ 8, be warming up to 15-30 DEG C, reaction 3-6 hour, react complete and obtain two step coupling solutions, for subsequent use;
F), de-ester reaction:
Maintain the temperature between 0-50 DEG C by two step coupling solutions of e) step gained, adjust pH=8 ~ 11, carry out de-ester reaction with 30%NaOH solution, reaction 4-8 hour, obtaining de-ester reaction liquid, is namely formula II blue active dye solution.
Preferably, the preparation method of this blue active dye also comprises the steps:
G), saltout:
In the de-ester reaction liquid of f) step gained, add NaCl, treat that dyestuff is separated out and filter, get filter cake and obtain dyestuff,
H), dry:
Drying g) collecting the filter cake obtained, pulverizing, obtaining dyestuff finished product.
In above-mentioned preparation method, the amino sulfuryl-naphthalidine of 4-beta-hydroxyethyl is by naphthalidine-4-sulfonic acid via acetylize, and chlorosulphonation, condensation, hydrolysis, saltout and obtain.Concrete working method is as follows:
D1), acetylize:
Dissolved by 55.75g naphthalidine-4-sulfonic acid, be warming up to 40 DEG C, under liquid, (below liquid level) drips 40.8g diacetyl oxide, is warming up to 60-65 DEG C in process, after reaction 15-20min, is cooled to 20-30 DEG C, adjusts pH=7-7.5, reaction 3-6 hour; Solution spray is dry, obtain 1-acetylaminohydroxyphenylarsonic acid 4-naphthene sulfonic acid dry product.
D2), chlorosulphonation:
Chlorsulfonic acid 116.5g is added in 1000ml four-hole bottle, by d1) 1-acetylaminohydroxyphenylarsonic acid 4-naphthene sulfonic acid dry product prepared by step, join in chlorsulfonic acid, stir, be warming up to 120 DEG C, react 4 hours, be cooled to 60 DEG C and add 68.4g sulfur oxychloride, react 2 hours, be warming up to 90-95 DEG C of insulation 0.5 hour, be warming up to 105-110 DEG C of insulation 0.5 hour again, be cooled to less than 40 DEG C, obtain chlorosulphonation feed liquid.In 3000ml beaker, add water 200ml, trash ice 500g adds chlorosulphonation feed liquid under stirring, and adds trash ice in good time and keeps system temperature lower than 0 DEG C, obtain solidliquid mixture.This solidliquid mixture is filtered, gets filter cake for subsequent use.
D3), condensation:
In 1000ml beaker, add water 200ml, Monoethanolamine MEA BASF 13.0g, stir to entirely molten, Monoethanolamine MEA BASF solution, by d2) filter cake prepared joins in Monoethanolamine MEA BASF solution, is warming up to 40-50 DEG C, keep pH=10-11, reaction 4-8 hour, obtains condensated liquid.
D4), be hydrolyzed:
At d3) in the condensated liquid prepared of step, add the NaOH solid of condensated liquid volume 3 ~ 4%, be warming up to 90-100 DEG C of reaction 3-6 hour, obtain hydrolyzed solution.
D5), saltout
At d4) hydrolyzed solution prepared of step adds Repone K, and the amino sulfuryl-naphthalidine of 4-beta-hydroxyethyl is separated out, and after the amino sulfuryl-naphthalidine of 4-beta-hydroxyethyl is separated out, filter, collect filter cake, detection level is for subsequent use.
Present invention also offers said structure formula I compound for purposes that is textile or dyeing nylon.
In the preparation method of above-claimed cpd and compound,
Para-ester also known as to (beta-sulfuric ester ethyl sulfonyl) aniline, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) sulfuric ester, 4-sulfovinic acid sulfuryl aniline, p-beta-hydroxy second sulfone aniline sulfuric ester or p-beta-hydroxy second sulfone aniline sulfuric ester, its structural formula is as follows:
Between position ester be between the abbreviation of (beta-sulfuric ester ethyl sulfonyl base) aniline, its structural formula is as follows:
H acid is the abbreviation of 1-amino-8-naphthol-3,6-disulfonate sodium, and its structural formula is as follows:
The structural formula of the amino sulfuryl-naphthalidine of 4-beta-hydroxyethyl is:
The structural formula of Monoethanolamine MEA BASF is NH
2cH
2cH
2oH.
The beneficial effect that the present invention has:
Reactive dyestuffs good water solubility of the present invention, has high-affinity under upper dye condition, and dyeing and printing process suitability is wide, and environmental pollution is little, coloured light is gorgeous, every use properties excellent and the free heavy metal of nothing.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but do not limit protection scope of the present invention.
Embodiment 1
A kind of azo 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 1000ml beaker, add 200ml water then the para-ester 28.1g of 100% amount is added, stir 15 minutes.Again 24.3 gram of 30% hydrochloric acid soln is added.Directly be less than 0 DEG C with ice adjustment solution temperature, under reaction soln guarantees that pH value is less than the condition of 2,30% sodium nitrite solution of 23.5g added fast.Holding temperature 0 ~ 5 DEG C, reacts 2 hours, remains congo-red test paper in blue after infiltrating, in blue after starch KI test paper infiltrates in reaction process.React complete thionamic acid and remove remaining nitrous acid, obtain diazo solution, for subsequent use.
B), H acid dissolve:
In 1000ml beaker, add water, add the H acid 34.2g of 100% amount, stir, adjust pH=6.5-7.5 with 30%NaOH solution, dissolve obtain H acid solution completely, for subsequent use.
C), a step coupling:
Joined by the H acid solution that b) prepared by step in diazo solution prepared by a) step, stirring reaction 4 hours, temperature 7-10 DEG C, obtains a step coupling solution, for subsequent use.
D), the amino sulfuryl-naphthalidine diazotization of 4-beta-hydroxyethyl
In 1000ml beaker, add 200ml water then amino for the 4-beta-hydroxyethyl of 100% amount sulfuryl-naphthalidine 34.6g is added, stir 15 minutes.Again 24.3g 30% hydrochloric acid soln is added.Directly be less than 0 DEG C with ice adjustment solution temperature, under reaction soln guarantees that pH value is less than the condition of 2,23.5g 30% sodium nitrite solution added fast.Holding temperature 0 ~ 5 DEG C, reacts 2 hours, remains congo-red test paper in blue after infiltrating, in blue after starch KI test paper infiltrates in reaction process.React complete thionamic acid and remove remaining nitrous acid, obtain diazotization liquid, for subsequent use.
E), two step couplings:
D) step is prepared diazotization liquid and joins step c) in the step coupling solution prepared, stir, use Na
2cO
3make acid binding agent, adjust pH=7 ~ 8, temperature 25 DEG C, reacts 4 hours, reacts complete and obtains two step coupling solutions, for subsequent use.
F), de-ester reaction:
Be warming up between 40-50 DEG C by two step coupling solutions of e) step gained, adjust pH=9 ~ 9.5 with 30%NaOH solution, carrying out de-ester reaction, react 4 hours, obtain de-ester reaction liquid, is namely formula III azo blue active dye solution.
G), saltout:
In the de-ester reaction liquid of f) gained, add NaCl saltout, wherein the ratio of sodium-chlor and de-ester reaction liquid is 0.05g:1mL, treats that dyestuff is separated out and filters, get filter cake and obtain dyestuff
H), dry:
Drying g) collecting the dyestuff filter-cakes obtained, pulverizing, obtaining dyestuff finished product 90g.
In above-mentioned preparation method, the amino sulfuryl-naphthalidine of 4-beta-hydroxyethyl is by naphthalidine-4-sulfonic acid via acetylize, and chlorosulphonation, condensation, hydrolysis, saltout and obtain.Concrete working method is as follows:
D1), acetylize:
Dissolved by 55.75g naphthalidine-4-sulfonic acid, be warming up to 40 DEG C, under liquid, (below liquid level) drips 40.8g diacetyl oxide, is warming up to 60-65 DEG C in process, after reaction 15-20min, is cooled to 20-30 DEG C, adjusts pH=7-7.5, react 5 hours; Solution spray is dry, obtain 1-acetylaminohydroxyphenylarsonic acid 4-naphthene sulfonic acid dry product.
D2), chlorosulphonation:
Chlorsulfonic acid 116.5g is added by d1 in 1000ml four-hole bottle) the 1-acetylaminohydroxyphenylarsonic acid 4-naphthene sulfonic acid dry product prepared of step, join in chlorsulfonic acid, stir, be warming up to 120 DEG C, react 4 hours, be cooled to 60 DEG C and add 68.4g sulfur oxychloride, react 2 hours, be warming up to 90-95 DEG C of insulation 0.5 hour, then be warming up to 105-110 DEG C of insulation 0.5 hour, be cooled to less than 40 DEG C, obtain chlorosulphonation feed liquid.In 3000ml beaker, add water 200ml, trash ice 500g adds chlorosulphonation feed liquid under stirring, and adds trash ice in good time and keeps system temperature lower than 0 DEG C, obtain solidliquid mixture.This solidliquid mixture is filtered, gets filter cake for subsequent use.
D3), condensation:
Water 200ml is added in 1000ml beaker, Monoethanolamine MEA BASF 13.0g, stirs to entirely molten, obtains Monoethanolamine MEA BASF solution, by d2) filter cake prepared, join in Monoethanolamine MEA BASF solution, be warming up to 40-50 DEG C, keep pH=10-11, reaction 4-8 hour, detecting with thin-layer chromatography, with steps d 2) content of product is less than 0.03 for terminal, obtains condensated liquid.
D4), be hydrolyzed:
At d3) in the condensated liquid prepared of step, add the NaOH solid of condensated liquid volume 3 ~ 4%, be warming up to 90-100 DEG C of reaction 4 hours, obtain hydrolyzed solution.
D5), saltout
At d4) hydrolyzed solution prepared of step adds the Repone K of its volume 10% amount, and the amino sulfuryl-naphthalidine of 4-beta-hydroxyethyl is separated out, and after the amino sulfuryl-naphthalidine of 4-beta-hydroxyethyl is separated out, filter, collect filter cake, detection level is for subsequent use.
Table one: nylon active blue performance, quality index
Table two: performance index contrast
Embodiment 2
Position ester between being changed to by para-ester in a) step of embodiment 1 preparation method, will obtain the blue active dye with following formula IV structure
Compound of the present invention and preparation method thereof is described by specific embodiment.Those skilled in the art can use for reference the links such as content appropriate change raw material of the present invention, processing condition and realize other object corresponding, its relevant change does not all depart from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included within scope of the present invention.
Claims (5)
1. a blue active dye, is characterized in that: this blue active dye has the general structure of 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 the blue active dye described in any one of claim 1-3, is characterized in that: comprise the steps:
A), para-ester or a position ester diazotization:
Xiang Shuizhong adds para-ester or a position ester, then adds ice and hydrochloric acid soln, adds sodium nitrite solution, carries out diazotization reaction, reacts complete thionamic acid and removes remaining nitrous acid, obtain diazo solution, for subsequent use;
B), H acid dissolve:
Xiang Shuizhong adds H acid, stirs, and adjusts pH=6.5-7.5 with 30%NaOH solution, obtains H acid solution after dissolving completely, for subsequent use;
C), a step coupling:
Joined by the H acid solution that b) prepared by step in diazo solution prepared by a) step, stirring reaction 3-4 hour, obtains a step coupling solution, for subsequent use;
D), the amino sulfuryl-naphthalidine diazotization of 4-beta-hydroxyethyl
In end water, add the amino sulfuryl-naphthalidine of 4-beta-hydroxyethyl, then add ice and hydrochloric acid soln, add sodium nitrite solution, carry out diazotization reaction, react complete thionamic acid and remove remaining nitrous acid, obtain diazotization liquid, for subsequent use;
E), two step couplings:
The diazotization liquid that d) prepared by step is joined step c) in the step coupling solution prepared, stir, use Na
2cO
3make acid binding agent, adjust pH=7 ~ 8, be warming up to 15-30 DEG C, reaction 3-6 hour, react complete and obtain two step coupling solutions, for subsequent use;
F), de-ester reaction:
Maintain the temperature between 0-50 DEG C by two step coupling solutions of e) step gained, adjust pH=8 ~ 11, carry out de-ester reaction with 30%NaOH solution, reaction 4-8 hour, obtaining de-ester reaction liquid, is namely blue active dye solution.
5. blue active dye according to claim 1 is used for purposes that is textile or dyeing nylon.
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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 (2)
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 |
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 |
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JPS59115360A (en) * | 1982-12-22 | 1984-07-03 | Sumitomo Chem Co Ltd | Disazo compound and method for dyeing fiber by using the same |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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