CN102504584A - Azo type blue reactive dye, and its preparation method and application - Google Patents
Azo type blue reactive dye, and its preparation method and application Download PDFInfo
- Publication number
- CN102504584A CN102504584A CN2011102997497A CN201110299749A CN102504584A CN 102504584 A CN102504584 A CN 102504584A CN 2011102997497 A CN2011102997497 A CN 2011102997497A CN 201110299749 A CN201110299749 A CN 201110299749A CN 102504584 A CN102504584 A CN 102504584A
- Authority
- CN
- China
- Prior art keywords
- acid
- solution
- preparation
- diazotization
- oso
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 *=C(C=C1)C2=CC=CCC2=C1N Chemical compound *=C(C=C1)C2=CC=CCC2=C1N 0.000 description 1
Landscapes
- Coloring (AREA)
Abstract
The invention relates to an azo type blue reactive dye, and its preparation method and application. 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 azo-type reactive dyestuffs, preparation method and application 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, and environmental pollution is little, coloured light is gorgeous, each item use properties excellent, does not have azo-type blue active dye, preparation method and the application thereof of free heavy metal.
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):
Work as R in the formula (I)
1For-H or-SO
3During M, R
2For-SO
2CH
2CH
2OSO
3M or-SO
2CH
2CH
2OH or-SO
2NHCH
2CH
2OSO
3M or-SO
2NHCH
2CH
2OH;
Work as R
1For-SO
2CH
2CH
2OSO
3M or-SO
2CH
2CH
2OH or-SO
2NHCH
2CH
2OSO
3M or-SO
2NHCH
2CH
2During OH; R
2For-H or-SO
3M;
M is-H or basic metal.Preferably, said M is-Na.
More preferably,
R described in the formula (I)
1For-H or-SO
3During M, R
2For-SO
2CH
2CH
2OSO
3M or-SO
2NHCH
2CH
2OSO
3M;
Said R
1For-SO
2CH
2CH
2OSO
3M or-SO
2NHCH
2CH
2OSO
3During M; R
2For-H or-SO
3M; M is-Na.
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, 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), diazotization
Xiang Shuizhong adds the arbitrary compound in the following structural formula (X-1)-(X-5), 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, promptly is blue active dye solution;
Preferably, the preparation method of this blue active dye also comprises the steps:
F), saltout:
To e) two steps of step gained add NaCl in the coupling solutions, treat that dyestuff separates out filtration, and get filter cake and get dyestuff,
G), drying:
With f) collect the filter cake obtain and dry, pulverize, the dyestuff finished product.
The structural formula information of formula (X-1)-(X-5) is following:
(X-1) 2-amino-6-naphthene sulfonic acid
(X-2) 6-beta-hydroxyethyl sulfonyl sulfuric ester-naphthalidine
(X-3) 6-beta-hydroxyethyl sulfonyl-naphthalidine
(X-4) 4-beta-hydroxyethyl sulfonyl imines sulfuric ester-naphthalidine
(X-5) 4-beta-hydroxyethyl sulfonyl imines-naphthalidine.
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 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 (II-1) structural formula:
The preparation method of formula (II-1) 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, promptly is blue active dye solution, and the structural formula of blue active dye is shown in (II-1).
F), saltout:
To e) add NaCl in the two step coupling solutions of step gained and saltout, wherein the ratio of NaCl and two step coupling solutions is 0.05g: 1mL; Treat that dyestuff separates out filtration, get filter cake and get dyestuff;
G), drying:
With f) the dyestuff filter cake that obtains of collection step dries, pulverize, the dyestuff finished product.
When diazo component became para-ester by a position ester in a) step, other steps were the same, will obtain having the blue active dye of following structural formula (II-2).
Embodiment 2
A kind of blue active dye has formula (III-1) structural formula:
The preparation method of formula (III-1) 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 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 solution, and is subsequent use.
B), H acid dissolving:
In the 1000ml beaker, add entry, add the H acid of 34.2g 100% amount again, stir, transfer pH=6.5-7.5, obtain the H acid solution after the dissolving fully with 30%NaOH solution, subsequent use.
C), a step coupling:
With b) the H acid solution of preparation joins in the diazotization solution of a) step preparation, stirring reaction 4 hours, temperature 7-10 ℃, a step coupling solution, subsequent use.
D), the diazotization of 6-beta-hydroxyethyl sulfonyl sulfuric ester-naphthalidine
In the 1000ml beaker, add 200ml water and then 100%6-beta-hydroxyethyl sulfonyl sulfuric ester-naphthalidine 33.1g 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) 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, promptly is formula (III-1) blue active dye solution.
F), saltout:
To e) add NaCl in the two step coupling solutions of step gained and saltout, wherein the ratio of NaCl and two step coupling solutions is 0.05g: 1mL; Treat that dyestuff separates out filtration, get filter cake and get dyestuff,
G), drying:
With f) collect the filter cake obtain and dry, pulverize, the dyestuff finished product.
Between diazo component is become by para-ester in a) step, during the ester of position, will obtain having blue active dye with following formula (III-2) structure.
In the aforesaid method, wherein via acetylize, reduce by chlorosulphonation by 1-amino-6-naphthene sulfonic acid for 6-beta-hydroxyethyl sulfonyl sulfuric ester-naphthalidine, hydroxyethylation, and esterification, dilution, hydrolysis, saltouing obtains.Concrete working method is following:
(d1), acetylize:
With 1-amino-6-naphthene sulfonic acid 56.3g 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, is warming up to 60 ℃ of reactions 4 hours; Solution spray is dry, obtain 1-acetylaminohydroxyphenylarsonic acid 6-naphthene sulfonic acid dry product.
(d2), chlorosulphonation:
In the 1000ml four-hole bottle, add the 1-acetylaminohydroxyphenylarsonic acid 6-naphthene sulfonic acid dry product of chlorsulfonic acid 116.5g, join in the chlorsulfonic acid, stir the preparation of (d1) step; Be warming up to 120 ℃, reacted 4 hours, be cooled to 60 ℃ and add the 68.5g 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), reduction:
In the 1000ml beaker, add entry 150ml, sodium sulfite anhy 96 311g stirs, and temperature is controlled at 25-30 ℃, and the filter cake adding with step (d2) preparation remains pH=7.5-8 in the process, use Na
2CO
3Make acid binding agent.Reacted 2 hours, and obtained the-sulfinic acid system, subsequent use
(d4), hydroxyethylation:
In the-sulfinic acid system that joins step (d3) preparation under the oxyethane liquid, stir, be warming up to 60 ℃, remain pH=7-7.5 in the process; Regulate with 25% sulphuric acid soln, reacted 10-15 hour, reaction finishes, and filters; Collect filter cake, dry, get hydroxyethylation thing dry product, subsequent use.
(d5), esterification:
In four-hole bottle, add 105% sulfuric acid 176.1g the hydroxyethylation thing dry product that step (d4) prepares is slowly added, temperature is controlled between 10-15 ℃, stirs, and temperature is slowly risen to 120 ℃ of reactions 4 hours, is cooled to below 40 ℃, gets the esterification feed liquid, and is for use.
(d6), dilution, hydrolysis:
In the 3000ml beaker, add entry 200ml, trash ice 500g stirring adds the esterification feed liquid of step (d5) preparation down, and add trash ice maintenance system temperature is 0-10 ℃ in good time, the existence of dilute sulphuric acid in dilution, kharophen is hydrolyzed to amino, gets diluent.
(d7), saltout
(ratio that refers to Repone K and diluent is 0.1g: 1mL) in the diluent of step (d6) preparation, to add the Repone K of diluent volume 10% amount; 6-beta-hydroxyethyl sulfonyl sulfuric ester-naphthalidine is separated out; After treating that 6-beta-hydroxyethyl sulfonyl sulfuric ester-naphthalidine is separated out; Filter, collect filter cake, detection level is subsequent use.
Embodiment 3
A kind of blue active dye has formula (IV-1) structural formula:
The preparation method of formula (IV-1) blue active dye comprises the steps:
A), para-ester diazotization:
In the 1000ml beaker, add 200ml water, the para-ester 28.1g with 100% amount adds then, stirs 15 minutes.Again 24.3 grams, 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 solution, and is subsequent use.
B), H acid dissolving:
In the 1000ml beaker, add entry, add the H acid of 34.2g 100% amount 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 preparation joins in the diazotization solution of a) step preparation, stirring reaction 4 hours, temperature 7-10 ℃, a step coupling solution, subsequent use.
D), the diazotization of 6-beta-hydroxyethyl sulfonyl-naphthalidine
In the 1000ml beaker, add 200ml water and then the 6-beta-hydroxyethyl sulfonyl-naphthalidine 25.1g 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) 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, promptly is formula (IV-1) blue active dye solution.
F), saltout:
To e) add NaCl in the two step coupling solutions of step gained and saltout, wherein the ratio of NaCl and two step coupling solutions is 0.05g: 1mL; Treat that dyestuff separates out filtration, get filter cake and get dyestuff,
G), drying:
With f) collect the filter cake obtain and dry, pulverize, the dyestuff finished product.
Between diazo component is become by para-ester in a) step, during the ester of position, will obtain having blue active dye with following formula (IV-2) structure.
In the aforesaid method, wherein the preparation method of 6-beta-hydroxyethyl sulfonyl-naphthalidine comprises the steps:
(d1), acetylize:
With 1-amino-6-naphthene sulfonic acid 56.3g 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, is warming up to 60 ℃ of reactions 4 hours; Solution spray is dry, obtain 1-acetylaminohydroxyphenylarsonic acid 6-naphthene sulfonic acid dry product.
(d2), chlorosulphonation:
In the 1000ml four-hole bottle, add the 1-acetylaminohydroxyphenylarsonic acid 6-naphthene sulfonic acid dry product of chlorsulfonic acid 116.5g, join in the chlorsulfonic acid, stir the preparation of (d1) step; Be warming up to 120 ℃, reacted 4 hours, be cooled to 60 ℃ and add the 68.5g 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), reduction:
In the 1000ml beaker, add entry 150ml, sodium sulfite anhy 96 311g stirs, and temperature is controlled at 25-30 ℃, and the filter cake adding with step (d2) preparation remains pH=7.5-8 in the process, use Na
2CO
3Make acid binding agent.Reacted 2 hours, and obtained the-sulfinic acid system, subsequent use
(d4), hydroxyethylation:
In the-sulfinic acid system that joins step (d3) preparation under the oxyethane liquid, stir, be warming up to 60 ℃, remain pH=7-7.5 in the process, regulate with 25% sulphuric acid soln, to react 10-15 hour, reaction finishes, and gets hydroxyethylation thing solution, and is subsequent use.
(d5), hydrolysis:
In the hydroxyethylation thing solution of step (d4) preparation, add the NaOH solid of hydroxyethylation thing liquor capacity 3～4%, be warming up to 90-100 ℃, reacted 6 hours, get hydrolyzed solution;
(d6), saltout
In the hydrolyzed solution of step (d5) preparation, add the Repone K of hydrolyzed solution volume 10% amount, 6-beta-hydroxyethyl sulfonyl-naphthalidine separated out, treat that 6-beta-hydroxyethyl sulfonyl-naphthalidine is separated out after, filter, collect filter cake, detection level is subsequent use.
Embodiment 4
A kind of azo-type blue active dye has the structural formula of formula (V-1),
The preparation method of formula (V-1) reactive dyestuffs 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 sulfuric ester-naphthalidine diazotization
In the 1000ml beaker, add 200ml water and then the 4-beta-hydroxyethyl sulfonyl imines sulfuric ester-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, promptly is formula (V-1) azo-type blue active dye solution.
F), saltout:
To e) add NaCl in the two step coupling solutions of gained and saltout, wherein the ratio of NaCl and two step coupling solutions is 0.05g: 1mL; Treat that dyestuff separates out filtration, get filter cake and get dyestuff
G), drying:
With f) collect the dyestuff filter cake obtain and dry, pulverize, the dyestuff finished product.
The position ester will obtain having the blue active dye as shown in the formula (V-2) structure between para-ester in the above-mentioned a) step is changed to
Among the above-mentioned preparation method, 4-beta-hydroxyethyl sulfonyl imines sulfuric ester-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 4 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, 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 sulfuric ester (NH
2CH
2CH
2OSO
3H) 29.7g stirs and dissolves to complete, gets Monoethanolamine MEA BASF sulfuric ester solution; With d2) preparation filter cake join in the Monoethanolamine MEA BASF sulfuric ester solution; Be warming up to 30-35 ℃, keep pH=7.5-8, reacted 20-24 hour; Detecting steps d 2 with thin-layer chromatography) 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 6 hours, hydrolyzed solution.
D5), saltout
At d4) hydrolyzed solution of step preparation adds Repone K, and 4-beta-hydroxyethyl sulfonyl imines sulfuric ester-naphthalidine is separated out, treat that 4-beta-hydroxyethyl sulfonyl imines sulfuric ester-naphthalidine is separated out after, filter, collect filter cake, detection level is subsequent use.
Embodiment 5
A kind of azo-type blue active dye has the structural formula of formula (VI-1),
The preparation method of formula (VI-1) 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, promptly is formula (VI-1) azo-type blue active dye solution.
F), saltout:
To e) add NaCl in the two step coupling solutions of gained and saltout, wherein the ratio of NaCl and two step coupling solutions is 0.05g: 1mL; Treat that dyestuff separates out filtration, get filter cake and get dyestuff
G), drying:
With f) collect the dyestuff filter cake obtain and dry, pulverize, the dyestuff finished product.
The position ester will obtain having the blue active dye as shown in the formula (VI-2) structure between the para-ester in the above-mentioned a) step is changed to
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 (NH
2CH
2CH
2OH) 13.0g stirs and dissolves to complete, Monoethanolamine MEA BASF solution, with d2) filter cake of preparation; 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 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 dyeing behavior of the structural formula that the foregoing description 1 makes (II-1) is as shown in the table:
Table one: the blue performance of nylon active, quality index
Table two: performance index contrast
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: these reactive dyestuffs have the general structure with following formula (I):
Work as R in the formula (I)
1For-H or-SO
3During M, R
2For-SO
2CH
2CH
2OSO
3M or-SO
2CH
2CH
2OH or-SO
2NHCH
2CH
2OSO
3M or-SO
2NHCH
2CH
2OH;
Work as R
1For-SO
2CH
2CH
2OSO
3M or-SO
2CH
2CH
2OH or-SO
2NHCH
2CH
2OSO
3M or-SO
2NHCH
2CH
2During OH; R
2For-H or-SO
3M; M is-H or basic metal.
2. blue active dye according to claim 1 is characterized in that: said M is-Na.
3. blue active dye according to claim 1 and 2 is characterized in that:
Said R
1For-H or-SO
3During M, R
2For-SO
2CH
2CH
2OSO
3M or-SO
2NHCH
2CH
2OSO
3M; Said R
1For-SO
2CH
2CH
2OSO
3M or-SO
2NHCH
2CH
2OSO
3During M; R
2For-H or-SO
3M; M is-Na.
4. the preparation method of the said blue active dye of claim 1 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), diazotization
Xiang Shuizhong adds the arbitrary compound in the following structural formula (X-1)-(X-5), 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;
The structural formula information of formula (X-1)-(X-5) is following:
(X-1) 2-amino-6-naphthene sulfonic acid
(X-2) 6-beta-hydroxyethyl sulfonyl sulfuric ester-naphthalidine
(X-3) 6-beta-hydroxyethyl sulfonyl-naphthalidine
(X-4) 4-beta-hydroxyethyl sulfonyl imines sulfuric ester-naphthalidine
(X-5) 4-beta-hydroxyethyl sulfonyl imines-naphthalidine
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, promptly is blue active dye solution;
Preferably, the preparation method of this blue active dye also comprises the steps:
F), saltout:
To e) two steps of step gained add NaCl in the coupling solutions, treat that dyestuff separates out filtration, and get filter cake and get dyestuff,
G), drying:
With f) 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110299749.7A CN102504584B (en) | 2011-09-28 | 2011-09-28 | The blue dyestuff of a kind of azo-type blue active, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110299749.7A CN102504584B (en) | 2011-09-28 | 2011-09-28 | The blue dyestuff of a kind of azo-type blue active, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504584A true CN102504584A (en) | 2012-06-20 |
| CN102504584B CN102504584B (en) | 2016-04-27 |
Family
ID=46216722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110299749.7A Active CN102504584B (en) | 2011-09-28 | 2011-09-28 | The blue dyestuff of a kind of azo-type blue active, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504584B (en) |
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 CN201110299749.7A patent/CN102504584B/en active Active
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102504584B (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102504585A (en) | Blue active dye, preparation method and application thereof | |
| CN102504584B (en) | The blue dyestuff of a kind of azo-type blue active, preparation method and application thereof | |
| CN111100478B (en) | Preparation method and application of blue dye with three active groups | |
| CN102391675B (en) | A kind of azo reactive dye and preparation method thereof | |
| CN105273437B (en) | Red reactive dye as well as preparation method and application thereof | |
| CN102337044B (en) | A kind of reactive dyestuffs and preparation method thereof | |
| CN102433027A (en) | Azo blue active dye and preparation method thereof | |
| CN104592786B (en) | A kind of new special deep reactive orange or weld and preparation method thereof | |
| CN104672949B (en) | A kind of novel chemically-reactive blue dyes and preparation method thereof | |
| CN104194394B (en) | A kind of Black reactive dye composition, preparation method and application | |
| CN102504586A (en) | Blue reactive dye and its preparation method | |
| CN110157216A (en) | A kind of dark blue reactive dye and its processing method | |
| CN101705019B (en) | Red reactive dye for wool and preparation method thereof | |
| CN107163615B (en) | A kind of environment-friendly type Weak acid red dyestuff and preparation method thereof | |
| CN110054910A (en) | A kind of Black reactive dye composition and its preparation method and application | |
| CN102876077A (en) | Black reactive dye and preparation method thereof | |
| CN101255282A (en) | Reactive dye compound and uses thereof | |
| CN101735652B (en) | Red reactive dye and preparation method thereof | |
| CN102433029B (en) | Reactive black dye mixture | |
| CN101735653B (en) | Red reactive dye for wool and preparation method thereof | |
| CN112876875B (en) | Disazo reactive yellow dye and preparation method and application thereof | |
| CN101735655B (en) | Red reactive dye for wool and preparation method thereof | |
| CN101705015B (en) | Orange active dye and preparation method thereof | |
| CN107805403A (en) | A kind of preparation method of faintly acid orchil | |
| CN108102425B (en) | A kind of spy's dark black active dyestuff, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20230131 Granted publication date: 20160427 |