CN102504586A - Blue reactive dye and its preparation method - Google Patents
Blue reactive dye and its preparation method Download PDFInfo
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- CN102504586A CN102504586A CN2011102999933A CN201110299993A CN102504586A CN 102504586 A CN102504586 A CN 102504586A CN 2011102999933 A CN2011102999933 A CN 2011102999933A CN 201110299993 A CN201110299993 A CN 201110299993A CN 102504586 A CN102504586 A CN 102504586A
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- diazotization
- ester
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Abstract
The invention relates to a blue reactive dye and its preparation method. The blue reactive dye has structural general formula (I), and has good water solubility, high affinity under dyeing conditions, wide applicability for a printing and dyeing process, less environmental pollution, brilliant hue, excellent service performances and no free heavy metals.
Description
Technical field
The present invention relates to a kind of reactive dyestuffs and preparation method thereof, especially a kind of blue active dye 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):
R in the formula
1For-H or-SO
3M; R
2For-H or-SO
3M; M is-H or basic metal.
Preferably, R in the formula (I)
1For-H or-SO
3M; R
2For-H or-SO
3M; M is-Na.
More preferably, R in the formula (I)
1For-SO
3M; R
2For-H; M is-Na.
More preferably, these reactive dyestuffs have the structural formula of formula (II):
The present invention also provides the preparation method of above-mentioned reactive dyestuffs, 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), 2-amino-6-naphthene sulfonic acid diazotization
Xiang Shuizhong adds 2-amino-6-naphthene sulfonic acid, adds ice and hydrochloric acid soln, adds sodium nitrite solution again, 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.
The present invention also provides structural formula (I) blue active dye 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 2-amino-6-naphthene sulfonic acid is following:
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 blue active dye has formula (III) structural formula:
The preparation method of formula (III) blue active dye comprises the steps:
A), a position ester diazotization:
In the 1000ml beaker, add 200ml water and then 100% position ester 28.1g is added, stirred 15 minutes, add 30% hydrochloric acid soln of 24.3g again.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; Be 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 100%H acid of 32.4g again, 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), 2-amino-6-naphthene sulfonic acid diazotization
In the 1000ml beaker, add 100%2-amino-6-naphthene sulfonic acid that 200ml water adds 22.5g then, 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; Be 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) 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 between 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 blue active dye solution, the structural formula of blue active dye is shown in (III).
G), saltout:
To f) add NaCl in the de-ester reaction liquid of step 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) the dyestuff filter cake that obtains of collection step dries, pulverize, dyestuff finished product 80g.
The dyeing behavior of the blue active dye that embodiment 1 makes is as follows:
Table one: the blue performance of nylon active, quality index
Table two: performance index contrast
Embodiment 2
When diazo component in a) step at embodiment 1 becomes para-ester by a position ester, other steps will obtain having the blue active dye of following structural formula (IV) with embodiment 1.
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 (6)
1. blue active dye, it is characterized in that: this blue active dye has the general structure with following formula (I):
R in the formula
1For-H or-SO
3M; R
2For-H or-SO
3M; M is-H or basic metal.
2. a kind of blue active dye according to claim 1 is characterized in that: said R
1For-H or-SO
3M; R
2For-H or-SO
3M; M is-Na.
3. a kind of blue active dye according to claim 1 and 2 is characterized in that: said R
1For-SO
3M; R
2For-H; M is-Na.
4. according to each described a kind of blue active dye of claim 1-3, it is characterized in that: these reactive dyestuffs have the structural formula of formula (II):
5. the preparation method of each described blue active dye of claim 1-4 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, adds sodium nitrite solution again, 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), 2-amino-6-naphthene sulfonic acid diazotization
Xiang Shuizhong adds 2-amino-6-naphthene sulfonic acid, adds ice and hydrochloric acid soln, adds sodium nitrite solution again, 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.
6. the said blue active dye of claim 1 is used for the purposes of cotton textiles or dyeing nylon.
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| CN2011102999933A CN102504586A (en) | 2011-09-28 | 2011-09-28 | Blue reactive dye and its preparation method |
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|---|---|---|---|
| CN2011102999933A CN102504586A (en) | 2011-09-28 | 2011-09-28 | Blue reactive dye and its preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327545A (en) * | 2014-10-13 | 2015-02-04 | 天津德凯化工股份有限公司 | Dark blue reactive dye |
| 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 |
Citations (6)
| 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 |
| CN1643079A (en) * | 2002-03-22 | 2005-07-20 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fiber-reactive azo dyes, their preparation and use |
| CN1643081A (en) * | 2002-03-22 | 2005-07-20 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fibre reactive azodyes, production and use thereof |
| CN1912014A (en) * | 2006-08-15 | 2007-02-14 | 大连华成中瑞科技有限公司 | Dark black active dyestuff having high colour fixing rate |
| 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 |
| CN101544849A (en) * | 2008-12-12 | 2009-09-30 | 天津市德凯化工有限公司 | Activated dye composition and preparation method thereof |
-
2011
- 2011-09-28 CN CN2011102999933A patent/CN102504586A/en active Pending
Patent Citations (6)
| 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 |
| CN1643079A (en) * | 2002-03-22 | 2005-07-20 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fiber-reactive azo dyes, their preparation and use |
| CN1643081A (en) * | 2002-03-22 | 2005-07-20 | 德意志戴斯达纺织品及染料两合公司 | Dye mixtures of fibre reactive azodyes, production and use thereof |
| 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 |
| CN1912014A (en) * | 2006-08-15 | 2007-02-14 | 大连华成中瑞科技有限公司 | Dark black active dyestuff having high colour fixing rate |
| CN101544849A (en) * | 2008-12-12 | 2009-09-30 | 天津市德凯化工有限公司 | Activated dye composition and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327545A (en) * | 2014-10-13 | 2015-02-04 | 天津德凯化工股份有限公司 | Dark blue reactive dye |
| 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 |
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Application publication date: 20120620 |