CN102863815A - Method for preparing active dye for blue wool - Google Patents
Method for preparing active dye for blue wool Download PDFInfo
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- CN102863815A CN102863815A CN2012102774332A CN201210277433A CN102863815A CN 102863815 A CN102863815 A CN 102863815A CN 2012102774332 A CN2012102774332 A CN 2012102774332A CN 201210277433 A CN201210277433 A CN 201210277433A CN 102863815 A CN102863815 A CN 102863815A
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Abstract
The invention discloses a method for preparing active dye for blue wool. The preparation method comprises the following steps of: performing first condensation reaction on bromamine acid which serves as a raw material and phenylene diamine, and performing acid refining, sulfonation, second condensation reaction and aftertreatment to obtain the active dye. The method is advanced and low in cost and causes light pollution to the environment. The dye prepared by the method has bromo-acrylamide groups, and under a slightly acidic condition, by being used together with Sibagol B, the active dye has a high reactivity with wool and a high fixation rate and meets the 'machine washable' high fastness requirement of International Wool Secretariat, so the active dye is quite high in market competitiveness.
Description
Technical field
The present invention relates to dye field, particularly a kind of blue reactive dye for wool and preparation method thereof and uses thereof.
Background technology
In recent years, when people constantly pursue high-quality, healthy living, current Dyestuff Market faces enormous challenge.Now general dyeing wool, the used dyestuff of cashmere are matching stain, acid mordant dye and metallized dye; Because with the material that these kinds of dyes are dyed, fastness is all not good enough, coloured light is not bery gorgeous, but also can bring pollution to environment.Enter 21 century, because the restriction of ecotope, requirement for dye uptake, degree of fixation and dyeing waste-water is more and more higher, conventional dyes can not satisfy the development in epoch again, environmental protection type dye has become the World Textile Market to the basic demand of dyestuff, with regard to dyeing, need now to have suitable affinity, the reactive dyestuffs of the easy flush away characteristic of non-fixing part.
Contain one or above active gene in the reactive dyestuff molecule structure, under certain condition can with fiber in some group, such as the amino generation chemical reaction in the hydroxyl in the cellulosic fibre, protein and the tynex, make between dyestuff and fiber to form covalent linkage and become " dyestuff-fiber " colored compound.Therefore, this class dyestuff is also referred to as chemically-reactive dyes, and domestic custom is called reactive dyestuffs.
Application number is that 200810154107.6 Chinese patent discloses a kind of dyestuff with following structure, it can satisfy woolen dyed demand on performance, but still there are the problems such as activity is not enough, color is gorgeous not, and can produce the copper-containing wastewater of a large amount of acidity in its preparation, and the efficiency ratio that these copper catalysts utilize is lower, does not meet the requirement of Green Chemistry; And reaction relates to high-temperature operation, when using the higher reaction temperatures operation, can affect reaction effect and repeatability; And the middle material cost of using is very high, is not suitable for industrial production.
Summary of the invention
The object of the invention provides a kind of blue reactive dye for wool and preparation method thereof, to solve the deficiencies in the prior art.
The blue reactive dye for wool of the present invention is a kind of dyestuff with larger market competitiveness, this dyestuff has high fixation rate, high fiber-dye bond stability, high-dissolvability and the plurality of advantages such as bright-coloured beautiful coloured light very, and the preparation process of this dyestuff is comparatively simple, reduce use to the environment harmful reagent with respect to traditional technology, can solve on the traditional technology hair with the large problem of dye wastewater amount.
Blue reactive dye for wool of the present invention is to have bromo acrylamide group, under slightly acidic condition, cooperate levelling agent Sai Baige B(Sibagol B) use, have with wool hyperergy, degree of fixation advantages of higher are arranged, satisfy the high fastness requirement of " Machine Washable " of International Wool Secretariat's proposition fully.
Blue reactive dye for wool of the present invention has following general structure:
Wherein, R is a kind of in the following formula:
M represents positively charged ion, comprises Na
+, K
+Deng metallic cation.
Preferably, M is Na.This moment, described blue reactive dye for wool structural formula can be formula (1):
Described blue reactive dye for wool structural formula can also be formula (2):
The preparation method of the blue reactive dye for wool of the present invention comprises the steps:
A, primary condensation reaction:
1. in the primary condensation reaction pot, put end water, be warming up to 70-90 ℃, drop into bromamine acid and make its dissolving;
2. adding the stirring of alkali and S-WAT dissolved it in 1 hour fully;
Employed alkali can be alkali-metal carbonate or the acid carbonates such as yellow soda ash, salt of wormwood, cesium carbonate, perhaps other water-soluble weak base, preferably yellow soda ash.
3. drop into powdery to () phenylenediamine, drop at twice again catalyzer after stirring, holding temperature 35-38 ℃, till being reacted to raw material and disappearing.The stirring that this reaction needed is good has not allowed particle heavy under agitation, otherwise can cause reaction not thorough in the reaction.TLC chromatography or HPLC monitoring are used in reaction, and termination reaction when raw material disappears is Red copper oxide, cuprous halide or palladium catalyst etc. during described catalyzer.When using palladium catalyst, although also can synthesize target product, can improve production cost, not have economic worth.
B, acid treating:
1. put end water at refining kettle, drop into and be cooled to 5-10 ℃ after the S-WAT stirring is dissolved it fully;
2. the primary condensation reaction thing is added wherein and temperature control 15-20 ℃ fast, add 20% hydrochloric acid again and transfer pH to 3.0-5.0, rear filtered and recycled filter cake is dried filter cake.
C, sulfonation reaction:
1. drop into 20% oleum and 98% sulfuric acid, temperature is cooled to 0-20 ℃.
2. 2. filter cake temperature control 5-30 ℃ of the above-mentioned steps b that adds oven dry.Add rear holding temperature 10-30 ℃ of reaction 1 hour.Intensification 25-30 ℃ is continued reaction 4-6 hour, does liquid-phase chromatographic analysis and confirms terminal point;
3. in sulfonation dilution pot, add ice, water, sulfonated bodies is slowly joined in the dilution pot 5-8 ℃ of control temperature.Add rear material and separate out, filter and reclaim filter cake.
D, consecutive condensation:
1. in the condensation pot, add end water, with c 3. filter cake drop into wherein, stirred 2 hours.
2. with adjusting PH with base to 5-9, returning charge adds until completely dissolved water and adjusts volume, employed alkali is water-soluble highly basic, comprises the alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide.
3. add 2,3-, two bromo propionyl chloros, keep pH at 5-8 after adding, temperature 10-30 ℃, reacting must the secondary condenses after 30-60 minute.
E, usefulness TLC chromatography monitoring reaction can confirm when raw material disappears that above-mentioned reaction solution terminal point arrives, and are warming up to 50-60 ℃.Remove and carry out spraying drying behind the insolubles and get product.
Employed 20% oleum is the commercially available sulfuric acid that contains 20% sulphur trioxide in the above-mentioned raw materials, and 98% vitriol oil is commercially available industrial raw material, and all the other raw materials are commercially available, and purity all reaches 98% or higher.
Among the above-mentioned preparation technology, the mass ratio of employed 20% oleum and 98% sulfuric acid is during sulfonation: 2.2-6:1.
Blue dyes is soluble in water, add the acetic acid of pH=4.5 and the damping fluid of sodium-acetate, A Baige FFA and Sai Baige B.Wool fiber with 5 parts of this solution impregnation.Solution with the submergence wool fiber is warming up to 99 ℃ gradually again, and ceaselessly fully rocks solution, and temperature was kept 1 hour after arriving 99 ℃, added 0.2 part of ammonia soln after 1 hour again, was cooled to 80 ℃, kept 30 minutes again.Then with dyeing washing, and oven dry, namely can obtain bright-coloured beautiful, washing fastness good, photostabilization is good blue dyeing and weaving thing.
The invention has the beneficial effects as follows:
1) technique is simply advanced, and related reaction conditions is all very gentle, and is not only easy to operate, has reduced the safety problem that occurs in producing, and energy-saving and emission-reduction, has reduced cost;
2) quantity of wastewater effluent reduces greatly, uses the catalyzer of small amount in the reaction, and the copper-containing acid waste water amount of generation greatly reduces;
3) prepared dyestuff has high colour-fast rate, high fiber-dye bond stability, high-dissolvability, high Exposure to Sunlight and the bright-coloured beautiful characteristics such as coloured light is arranged, and is the high-grade hair dyestuff with certain market competitiveness.
Embodiment
Below by some preferred embodiments the present invention is further explained, these embodiment make an explanation to the present invention, rather than protection scope of the present invention is formed any restriction.
The following embodiment 1-4 of preparation of dyestuff method of the present invention:
Embodiment 1 preparation blue active dye 1 operates by following step:
A, primary condensation reaction:
1. in the primary condensation reaction pot, put end water 1500L, be warming up to 80 ℃, drop into the 100kg bromamine acid and make its dissolving;
2. add 60kg yellow soda ash and 16.5kg S-WAT and stirred 1 hour, it is dissolved fully;
3. drop into powdery Ursol D 35kg, stirring reaction divides two equal portions to drop into cuprous chloride 5kg again after 1 hour, holding temperature 35-36 ℃, reacts and disappears to raw material in 5 hours.This reaction will have good stirring, and the thing that do not allow in the reaction to respond sinks to the reactor bottom, otherwise can cause reaction not thorough.Do at last the monitoring of TLC chromatography, confirm raw material disappearance termination reaction.
B, acid treating:
1. put end water 1500L at refining kettle, drop into S-WAT 17kg and stirred 3 hours, be cooled to 5-7 ℃ after it is dissolved fully;
2. the primary condensation reaction thing was added wherein fast with 15-20 minute and control temperature at 17 ℃.Add 20% hydrochloric acid again and transfer pH to 3.0-3.2, filtered and recycled filter cake after 30 minutes is dried filter cake.
C, sulfonation reaction:
1. drop into 20% oleum 500L and 98% sulfuric acid 170L, temperature is cooled to 0-5 ℃;
2. the above-mentioned steps b that adds oven dry is filter cake 2., temperature control 5-8 ℃.Add rear holding temperature 10-12 ℃ of reaction 1 hour.Intensification 25-27 ℃ is continued reaction 4-6 hour, does liquid-phase chromatographic analysis and confirms terminal point;
3. in sulfonation dilution pot, add ice, water, sulfonated bodies is slowly joined in the dilution pot 5-8 ℃ of control temperature.Add rear material and separate out, carry out press filtration with membrane pressure filter, reclaim filter cake.
D, consecutive condensation:
1. in the condensation pot, add end water 2300L, with c 3. filter cake drop into wherein, stirred 2 hours.
2. transfer pH to 7.5 with sodium hydroxide, after filter cake dissolves fully, add water and adjust volume to 3000L.
3. slowly added 120kg 2 with 3 hours, 3-two bromo propionyl chloros are kept pH to 5.0-5.5 after adding, 15 ℃ of temperature, and reacting must the secondary condenses after 30 minutes.
E, usefulness TLC chromatography monitoring reaction can confirm when raw material disappears that above-mentioned reaction solution terminal point arrives, and are warming up to 50 ℃.Cross to filter out and carry out the spraying drying blue active dye 1 that gets product behind the insolubles, its structural formula as the formula (1).
Embodiment 2 preparation blue active dyes 2 operate by following step:
A, primary condensation reaction:
1. in the primary condensation reaction pot, put end water 2500L, be warming up to 80 ℃, drop into the 200kg bromamine acid and make its dissolving;
2. add 130kg yellow soda ash and 33kg S-WAT and stirred 1 hour, it is dissolved fully;
3. drop into powdery mphenylenediamine 80kg, divide again two equal portions to drop into cuprous iodide 8kg after stirring half an hour, holding temperature 35-38 ℃, react and disappeared to raw material in 5 hours.The thing that do not allow in the reaction to respond sinks to the reactor bottom, does at last the TLC chromatography and confirms terminal point.
B, acid treating:
1. put end water 3000L at refining kettle, drop into S-WAT 50kg, stir and be cooled to 9-10 ℃ after it being dissolved fully in 3 hours.
2. the primary condensation reaction thing was added wherein fast with 15-20 minute and control temperature at 18-20 ℃.Add 20% hydrochloric acid again and transfer pH to 3.5-4, filtered and recycled filter cake after 30 minutes is dried filter cake.
C, sulfonation reaction:
1. drop into 20% oleum 800L and 98% sulfuric acid 350L, temperature is cooled to 0-15 ℃.
2. the above-mentioned steps b that adds oven dry is filter cake 2., temperature control 8-10 ℃.Add 10 ℃ of reactions of rear holding temperature 1 hour.Heat up 28 ℃ and continue reaction 4 hours, do liquid-phase chromatographic analysis and confirm terminal point.
3. in sulfonation dilution pot, add ice, water, sulfonated bodies is slowly joined in the dilution pot 5-8 ℃ of control temperature.Add rear material and separate out, carry out press filtration with membrane pressure filter, reclaim filter cake.
D, consecutive condensation:
1. in the condensation pot, add end water 4500L, with c 3. filter cake drop into wherein, stirred 3 hours.
2. transfer pH to 7.5 with sodium hydroxide, after filter cake dissolves fully, add water and adjust volume to 5000L.。
3. slowly added 260kg 2 with 3 hours, 3-two bromo propionyl chloros are kept pH to 5.5 after adding, and temperature 10-12 ℃, reacting must the secondary condenses after 50 minutes.
E, usefulness TLC chromatography monitoring reaction can confirm when raw material disappears that above-mentioned reaction solution terminal point arrives, and are warming up to 60 ℃.Cross to filter out and carry out the spraying drying blue active dye 2 that gets product behind the insolubles, its structural formula as the formula (2).
Embodiment 3 preparation blue active dyes 1 operate by following step:
A, primary condensation reaction:
1. in the primary condensation reaction pot, put end water 1500L, be warming up to 70 ℃, drop into the 100kg bromamine acid and make its dissolving;
2. add 60kg yellow soda ash and 16.5kg S-WAT and stirred 1 hour, it is dissolved fully;
3. drop into powdery Ursol D 35kg, stirring reaction divides two equal portions to drop into cuprous chloride 5kg again after 1 hour, holding temperature 35-36 ℃, reacts and disappears to raw material in 5 hours.This reaction will have good stirring, and the thing that do not allow in the reaction to respond sinks to the reactor bottom, otherwise can cause reaction not thorough.Do at last the TLC monitoring, confirm raw material disappearance termination reaction.
B, acid treating:
1. put end water 1500L at refining kettle, drop into and be cooled to 5-7 ℃ after S-WAT 17kg stirring dissolved it in 3 hours fully;
2. the primary condensation reaction thing was added wherein fast with 15-20 minute and temperature control at 17 ℃.Add 20% hydrochloric acid again and transfer pH to 3.0-3.2, filtered and recycled filter cake after 30 minutes is dried filter cake.
C, sulfonation reaction:
1. drop into 20% oleum 1020L and 98% sulfuric acid 170L, temperature is cooled to 0-5 ℃;
2. the above-mentioned steps b that adds oven dry is filter cake 2., temperature control 10-30 ℃.Add rear holding temperature 10-30 ℃ of reaction 1 hour.Intensification 25-27 ℃ is continued reaction 4-6 hour, does liquid-phase chromatographic analysis and confirms terminal point;
3. in sulfonation dilution pot, add ice, water, sulfonated bodies is slowly joined in the dilution pot 5-8 ℃ of control temperature.Add rear material and separate out, carry out press filtration with membrane pressure filter, reclaim filter cake.
D, consecutive condensation:
1. in the condensation pot, add end water 2300L, with c 3. filter cake drop into wherein, stirred 2 hours.
2. transfer pH to 7.5 with sodium hydroxide, after filter cake dissolves fully, add water and adjust volume to 3000L.
3. slowly added 120kg 2 with 3 hours, 3-two bromo propionyl chloros are kept pH to 5.0-5.5 after adding, 15 ℃ of temperature, and reacting must the secondary condenses after 30 minutes.
E, usefulness TLC chromatography monitoring reaction can confirm when raw material disappears that above-mentioned reaction solution terminal point arrives, and are warming up to 50 ℃.Cross to filter out and carry out the spraying drying blue active dye 1 that gets product behind the insolubles, its structural formula as the formula (1).
Embodiment 4 preparation blue active dyes 2 operate by following step:
A, primary condensation reaction:
1. in the primary condensation reaction pot, put end water 2500L, be warming up to 90 ℃, drop into the 200kg bromamine acid and make its dissolving;
2. add 130kg yellow soda ash and 33kg S-WAT and stirred 1 hour, it is dissolved fully;
3. drop into powdery mphenylenediamine 80kg, divide again two equal portions to drop into Red copper oxide 8kg after stirring half an hour, holding temperature 35-38 ℃, react and disappeared to raw material in 5 hours.Do not allowed particle heavy under agitation in the reaction, done at last TLC thin plate chromatography and confirm terminal point.
B, acid treating:
1. put end water 3000L at refining kettle, drop into S-WAT 50kg, stir and be cooled to 9-10 ℃ after it being dissolved fully in 3 hours.
2. the primary condensation reaction thing was added wherein fast with 15-20 minute and temperature control at 18-20 ℃.Add 20% hydrochloric acid again and transfer pH to 3.5-4, filtered and recycled filter cake after 30 minutes is dried filter cake.
C, sulfonation reaction:
1. drop into 20% oleum 800L and 98% sulfuric acid 350L, temperature is cooled to 10-20 ℃.
2. the filter cake that adds oven dry, temperature control 8-10 ℃.Add 10 ℃ of reactions of rear holding temperature 1 hour.Heat up 28 ℃ and continue reaction 4 hours, do liquid-phase chromatographic analysis and confirm terminal point.
3. in sulfonation dilution pot, add ice, water, sulfonated bodies is slowly joined in the dilution pot 5-8 ℃ of control temperature.Add rear material and separate out, carry out press filtration with membrane pressure filter, reclaim filter cake.
D, consecutive condensation:
1. in the condensation pot, add end water 4500L, with c 3. filter cake drop into wherein, stirred 3 hours.
2. transfer pH to 7.5 with potassium hydroxide, after filter cake dissolves fully, add water and adjust volume to 5000L.。
3. slowly added 260kg 2 in 3 hours consuming time, 3-two bromo propionyl chloros are kept pH to 5.5 after adding, and temperature 15-30 ℃, reacting must the secondary condenses after 50 minutes.
E, use the TLC monitoring reaction, can confirm when raw material disappears that above-mentioned reaction solution terminal point arrives, and is warming up to 60 ℃.Cross to filter out and carry out the spraying drying blue active dye 2 that gets product behind the insolubles, its structural formula as the formula (2).
Following examples are the application of dyestuff of the present invention, and its test data sees Table 1:
Embodiment 5 dyeing:
0.2 part of blue dyes (1) is dissolved in 113 parts of water, adds the acetic acid of 5 parts of pH=4.5 and the damping fluid of sodium-acetate, 2.5 parts of A Baige FFA and 4 parts of Sai Baige B.Wool fiber with 5 parts of this solution impregnation.Solution with the submergence wool fiber is warming up to 99 ℃ gradually again, and ceaselessly fully rocks solution, and temperature was kept 1 hour after arriving 99 ℃, added 0.2 part of ammonia soln after 1 hour again, was cooled to 80 ℃, kept 30 minutes again.Then with dyeing washing, and oven dry, obtain bright-coloured beautiful, washing fastness good, photostabilization is good blue dyeing and weaving thing.
Embodiment 6 dyeing:
0.4 part of blue dyes (1) is dissolved in 227 parts of water, adds the acetic acid of 10 parts of pH=4.5 and the damping fluid of sodium-acetate, 5 parts of A Baige FFA and 8 parts of Sai Baige B.Wool fiber with 10 parts of this solution impregnation.Solution with the submergence wool fiber is warming up to 99 ℃ gradually again, and ceaselessly fully rocks solution, and temperature was kept 1 hour after arriving 99 ℃, added 0.3 part of ammonia soln after 1 hour again, was cooled to 80 ℃, kept 30 minutes again.Then with dyeing washing, and oven dry, obtain bright-coloured beautiful, washing fastness good, photostabilization is good blue dyeing and weaving thing.
Embodiment 7 dyeing:
0.6 part of blue dyes (1) is dissolved in 340 parts of water, adds the acetic acid of 15 parts of pH=4.5 and the damping fluid of sodium-acetate, 7.5 parts of A Baige FFA and 12 parts of Sai Baige B.Wool fiber with 15 parts of this solution impregnation.Solution with the submergence wool fiber is warming up to 99 ℃ gradually again, and ceaselessly fully rocks solution, and temperature was kept 1 hour after arriving 99 ℃, added 0.5 part of ammonia soln after 1 hour again, was cooled to 80 ℃, kept 30 minutes again.Then with dyeing washing, and oven dry, obtain bright-coloured beautiful, washing fastness good, photostabilization is good blue dyeing and weaving thing.
Embodiment 8 dyeing:
0.2 part of blue dyes (2) is dissolved in 113 parts of water, adds the acetic acid of 5 parts of pH=4.5 and the damping fluid of sodium-acetate, 2.5 parts of A Baige FFA and 4 parts of Sai Baige B.Wool fiber with 5 parts of this solution impregnation.Solution with the submergence wool fiber is warming up to 99 ℃ gradually again, and ceaselessly fully rocks solution, and temperature was kept 1 hour after arriving 99 ℃, added 0.2 part of ammonia soln after 1 hour again, was cooled to 80 ℃, kept 30 minutes again.Then with dyeing washing, and oven dry, obtain bright-coloured beautiful, washing fastness good, photostabilization is good blue dyeing and weaving thing.
Embodiment 9 dyeing:
0.4 part of blue dyes (3) is dissolved in 227 parts of water, adds the acetic acid of 10 parts of pH=4.5 and the damping fluid of sodium-acetate, 5 parts of A Baige FFA and 8 parts of Sai Baige B.Wool fiber with 10 parts of this solution impregnation.Solution with the submergence wool fiber is warming up to 99 ℃ gradually again, and ceaselessly fully rocks solution, and temperature was kept 1 hour after arriving 99 ℃, added 0.3 part of ammonia soln after 1 hour again, was cooled to 80 ℃, kept 30 minutes again.Then with dyeing washing, and oven dry, obtain bright-coloured beautiful, washing fastness good, photostabilization is good blue dyeing and weaving thing.
Embodiment 10 dyeing:
0.6 part of blue dyes (4) is dissolved in 340 parts of water, adds the acetic acid of 15 parts of pH=4.5 and the damping fluid of sodium-acetate, 7.5 parts of A Baige FFA and 12 parts of Sai Baige B.Wool fiber with 15 parts of this solution impregnation.Solution with the submergence wool fiber is warming up to 99 ℃ gradually again, and ceaselessly fully rocks solution, and temperature was kept 1 hour after arriving 99 ℃, added 0.5 part of ammonia soln after 1 hour again, was cooled to 80 ℃, kept 30 minutes again.Then with dyeing washing, and oven dry, obtain bright-coloured beautiful, washing fastness good, photostabilization is good blue dyeing and weaving thing.
The blue reactive dye for wool application performance table of table 1 the present invention preparation
Claims (5)
1. the preparation method of a blue reactive dye for wool is characterized in that, described method comprises the steps:
A, primary condensation reaction:
1. in the primary condensation reaction pot, put end water, be warming up to 70-90 ℃, drop into bromamine acid and make its dissolving;
2. add alkali and S-WAT, stir and make its dissolving;
3. drop into phenylenediamine, after mixing, drop into catalyzer, holding temperature is at 35-38 ℃, termination reaction when raw material disappears;
B, acid treating:
1. put end water at refining kettle, drop into S-WAT, be cooled to 5-10 ℃ after stirring is dissolved it fully;
2. above-mentioned condensation reaction thing is added wherein, and temperature control 15-20 ℃, adding mass concentration is to filter after 20% hydrochloric acid is adjusted pH to 3.0-5.0 again, reclaims filter cake and oven dry;
C, sulfonation reaction:
1. drop into 20% oleum and 98% sulfuric acid, be cooled to 0-20 ℃;
2. add the filter cake that 2. the above-mentioned steps b of oven dry obtains, temperature control 5-30 ℃; Add rear holding temperature 10-30 ℃ of reaction 1 hour, be warming up to 25-30 ℃ of continuation react disappear to raw material till;
3. add ice, water in sulfonation dilution pot, sulfonated bodies is slowly joined in the dilution pot, the control temperature is at 5-8 ℃; Add rear material and separate out, filter and reclaim filter cake;
D, consecutive condensation:
1. in the condensation pot, add end water, with c 3. filter cake drop into wherein;
2. with adjusting PH with base to 5-9, after filter cake dissolves fully, add water and adjust volume;
3. add 2,3-, two bromo propionyl chloros, keep pH at 5-8 after adding, temperature is reacted to get the secondary condenses at 10-30 ℃;
E, raw material are warming up to 50-60 ℃ after disappearing, and cross to filter out and carry out spraying drying behind the insolubles and get product; The alkali of step a described in 2. is weak base, comprises at least one or more of following material: alkali-metal carbonate, alkali-metal acid carbonate;
The alkali of step b described in 2. comprises one or more of following material: sodium hydroxide, potassium hydroxide, lithium hydroxide at least;
Described catalyzer comprises one or more in the following material at least: cuprous halide, Red copper oxide, palladium catalyst;
The phenylenediamine of step a described in 3. is Ursol D or mphenylenediamine.
2. method according to claim 1 is characterized in that, the alkali of step a described in 2. is yellow soda ash.
3. method according to claim 1 is characterized in that, the alkali of step b described in 2. is sodium hydroxide.
4. method according to claim 1 is characterized in that, the mass ratio of 20% oleum described in the sulfonation reaction and 98% sulfuric acid is 2.2-6:1.
5. the prepared blue active dye of either method according to claim 1～4.
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| CN104788993A (en) * | 2015-05-12 | 2015-07-22 | 上海安诺其集团股份有限公司 | Dark blue dye composition for hair and preparation method thereof |
| CN104846661A (en) * | 2015-05-12 | 2015-08-19 | 上海安诺其集团股份有限公司 | Application of wool dark blue dye combination to wool or wool fabric dyeing |
| CN109012670A (en) * | 2018-09-05 | 2018-12-18 | 杭州下沙恒升化工有限公司 | Cu2Application method of the O in bromamine acid and aromatic amine compounds synthetic reaction |
| CN109206941A (en) * | 2018-09-05 | 2019-01-15 | 杭州下沙恒升化工有限公司 | A kind of preparation method of Vickery blue finished product |
| CN109825109A (en) * | 2019-03-25 | 2019-05-31 | 盐城工业职业技术学院 | A kind of mao with dyestuff, preparation method and its colouring method |
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| CN104788992A (en) * | 2015-03-04 | 2015-07-22 | 苏州大学 | Alpha-bromoacrylamide reactive group hemicyanine fluorescent active dye and preparation method thereof |
| CN104788992B (en) * | 2015-03-04 | 2017-07-07 | 苏州大学 | A kind of α bromos acrylamide reactive group half flower cyanines vital fluorescence dye and preparation method |
| CN104788993A (en) * | 2015-05-12 | 2015-07-22 | 上海安诺其集团股份有限公司 | Dark blue dye composition for hair and preparation method thereof |
| CN104846661A (en) * | 2015-05-12 | 2015-08-19 | 上海安诺其集团股份有限公司 | Application of wool dark blue dye combination to wool or wool fabric dyeing |
| CN109012670A (en) * | 2018-09-05 | 2018-12-18 | 杭州下沙恒升化工有限公司 | Cu2Application method of the O in bromamine acid and aromatic amine compounds synthetic reaction |
| CN109206941A (en) * | 2018-09-05 | 2019-01-15 | 杭州下沙恒升化工有限公司 | A kind of preparation method of Vickery blue finished product |
| CN109825109A (en) * | 2019-03-25 | 2019-05-31 | 盐城工业职业技术学院 | A kind of mao with dyestuff, preparation method and its colouring method |
| WO2021248809A1 (en) * | 2020-06-08 | 2021-12-16 | 浙江越新印染有限公司 | Red dye composition and use thereof for supercritical carbon dioxide waterless dyeing |
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