CN101418136A - Blue reactive dyes for wool and preparation method thereof - Google Patents
Blue reactive dyes for wool and preparation method thereof Download PDFInfo
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- CN101418136A CN101418136A CNA200810152920XA CN200810152920A CN101418136A CN 101418136 A CN101418136 A CN 101418136A CN A200810152920X A CNA200810152920X A CN A200810152920XA CN 200810152920 A CN200810152920 A CN 200810152920A CN 101418136 A CN101418136 A CN 101418136A
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Abstract
The invention discloses blue wool reactive dye and a preparation method thereof. The general formula of the dye is as shown (on the lower right). The preparation method for the blue reactive dye comprises the following steps: copper phthalocyanine, a chlorosulfonic acid, thionyl chloride, ethanolamine and oleum are taken as main raw materials, and the blue wool reactive dye is prepared by chlorosulfonation, condensation, esterification, improvement of the concentration of the dye, adjustment of the chromatic light, adjustment of the strength, drying and packaging. The blue wool reactive dye obtained has higher reactivity, superior solubility, colorful chromatic light, good lightfastness performance and high exhaustion rate and fixation rate, and does not contain free metal ions and chemical raw materials which are strictly prohibited to be used. By adoption of the pre-mixing technology after film treatment, waste water and waste residue can be prevented from being generated, so that the blue wool reactive dye greatly promotes environmental protection.
Description
Technical field
The present invention relates to a kind of reactive dye for wool and preparation method thereof, especially hair blue active dye and preparation method thereof.
Background technology
Now general dyeing wool, cashmere, used dyestuff 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 really gorgeous, but also can cause trouble to environmental protection.Enter 21 century, because the restriction of environmental ecology is more and more higher for the requirement of dye uptake, degree of fixation and dyeing waste-water.Matching stain can not satisfy development of times again.
Summary of the invention
Technical problem to be solved by this invention is, provides one can reduce environmental pollution, and the desired raw material cost is low, product solubility height, and bright in colour, and the application performance excellence, easy to use, the strong hair of suitability is with blue active dye and preparation method thereof.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: use blue active dye for a kind of mao, have following general structure
Wherein
3.5≦X+Y≦4
M represents basic metal, is preferably sodium or potassium, more preferably sodium;
R＝—NH-R
3 —NH-R
2OSO
3M
In a kind of.
In R,
R
1Identical or different, and expression C
1-6Alkyl, preferred C
1-4Alkyl, methyl more preferably;
R
2Identical or different, and expression C
1-6Alkyl, preferred C
1-4Alkyl, ethyl more preferably;
R
3Identical or different, and expression C
2-4Thiazolinyl, be preferably vinyl;
X
1Identical or different, and expression halogen, preferably each X
1Identical and the expression bromine.
More preferably, in the above-mentioned general formula compound, M is a sodium, each R
1Identical and be methyl; Each R
2Identical and be ethyl; Each R
3Identical and be vinyl; Each X
1Identical and the expression bromine.
In addition, the present invention also provides the preparation method of above-mentioned hair with blue active dye, comprises the steps:
A. CuPc and chlorsulfonic acid are carried out chlorosulfonation, crystallisation by cooling separates then, obtains CuPc chlorosulphonation thing;
Preferably, crystallisation by cooling adopts ice to analyse.Separate and adopt solid-liquid separator to finish.
B. condensation reaction: with the mass percent concentration of solution is chlorosulphonation thing and Monoethanolamine MEA BASF 5-40%, that a step obtains, and catalyzer and acid binding agent mix, and in pH=1.0～12.0,10-80 ℃ was reacted 8-16 hour down; The auxiliary agent that adds 1-25% (volume) again stirs and carries out solid-liquid separation, and oven dry obtains dry condensed products.
Preferably, first-selected Monoethanolamine MEA BASF and the catalyzer of adding.Adjust 10～80 ℃ of temperature.Add acid binding agent, and in pH=1.0～12.0 time, reacted 12 hours.
C. esterification: the condensed products of step b gained through esterification, is cooled off, Crystallization Separation then, make carboxylate;
Preferably, adopt sulfuric acid, carry out esterification as the oleum of 98-120%.Preferred esterification condition is :-10 ℃ to 100 ℃, the reaction times is 5-8 hour.
Preferred cooling, Crystallization Separation are :-10 ℃ to 40 ℃, stir and carried out solid-liquid separation 2-4 hour.
D. alkaline purification reaction: in the carboxylate feed liquid of step c gained, add acid binding agent, and pH=11.0～13.0 ,-10～40 ℃, reacted 0.5-2 hour; Then, pH is adjusted to 5.0-8.0, obtains look liquid; This look liquid is hair blue dyes of the present invention.
Preferably, the alkaline purification reaction times is 1 hour, adopt mineral acid with pH regulator to 5.0-8.0; More preferably adopt 30% salt acid for adjusting pH value.
Preferably, also can comprise step e in addition.
E. remove insolubles: in the look liquid of steps d gained, add diatomite, and carry out solid-liquid separation; Make filtrate then behind membrane filtration, obtain the look liquid of C%=10-50%.
More preferably, in solid-liquid separator, separate.After the separation, washery refuse is removed insolubles, collects filtrate, and filtrate is carried out membrane filtration, makes look liquid concentration C %=10～50%.
Preferably, also can comprise step f in addition.
F. piece together before and mix: the look liquid to step e gained carries out spraying drying, and dyeing is carried out coloured light and intensity adjustment according to coloration result again.To those skilled in the art, coloured light and intensity adjustment are conspicuous, need not to make creative work.
More preferably, with small-sized spray tower drying, the adjustment of coloured light and intensity is carried out in dyeing again according to coloration result with the look liquid of step e gained.Wherein, use glucose and/or Sodium sulfate anhydrous.min(99) to carry out the intensity adjustment.Its consumption is suitably adjusted according to the performance requriements of dyestuff, and these adjust the scope that belongs to conventional design to those skilled in the art, are conspicuous.
In addition, described preparation method can also comprise the steps:
G. dry: the look liquid to step e gained carries out spraying drying, and described spraying drying condition is conspicuous to those skilled in the art, to obtain hair blue active dye product.
More preferably, the look liquid of step e gained is joined in the feed liquid preheater, adjust 210 ℃ of inlet temperatures, 90～100 ℃ of temperature outs are carried out spraying drying, obtain hair blue active dye product.
More preferably:
Described step a is: add CuPc in chlorsulfonic acid, stir.0～100 ℃ of controlled temperature added CuPc in 1～2 hour consuming time.Adjust 100～140 ℃ of temperature, reacted 2 hours.Adjust 10～80 ℃ of temperature, 10～80 ℃ of holding temperatures added sulfur oxychloride in 1～2 hour consuming time.10～80 ℃ of holding temperatures were reacted 2 hours.Adjust 80～100 ℃ of temperature.80～100 ℃ of holding temperatures were reacted 1 hour.Adjust 100～130 ℃ of temperature, 100～130 ℃ of holding temperatures were reacted 1 hour.
Adjust 0～100 ℃ of temperature, follow trash ice to join ice resulting chlorosulphonation feed liquid and analyse in the jar, controlled temperature-10～40 ℃.1～2 hour consuming time, the chlorosulphonation feed liquid is added.Holding temperature-10～40 ℃ stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.With temperature-10～40 ℃ water washing filter cake, remove spent acid.Collect filter cake.Filtrate is deposited in the spent acid storage tank.
Described step b is: with the prepared chlorosulphonation thing of step a filter cake thin up, the mass percent concentration that makes solution is 5～40%.Stir down,, add catalyzer simultaneously the disposable adding of Monoethanolamine MEA BASF.Adjust 10～80 ℃ of temperature.Add acid binding agent, adjust pH=1.0～12.0,10～80 ℃ of holding temperatures were reacted 12 hours.And 1～25% adding auxiliary agent by volume, stir, join in the solid-liquid separator, separate.Collect filter cake, filter cake is dried, and dry product is weighed.
Described step c is: the prepared dry product of step b is joined in 98～120% oleums.Controlled temperature-10～20 ℃ added dry product in 1～2 hour consuming time.Adjust 20～100 ℃ of temperature.20～100 ℃ of holding temperatures were reacted 5 hours.
Adjust 0～40 ℃ of temperature, follow trash ice to join ice the carboxylate feed liquid of gained and analyse in the jar.Controlled temperature-10～40 ℃ added the carboxylate feed liquid in 1～2 hour consuming time.Holding temperature-10～40 ℃ stirred 1 hour.
Described steps d is: with the carboxylate feed liquid of step c gained, adjust temperature-10～40 ℃, add acid binding agent and adjust pH=11.0～13.0, holding temperature-10～40 ℃ is kept pH=11.0～13.0, reacts 1 hour.Adjust pH=5.0～8.0 with 30%HCl.
Described step e is: the resulting look liquid of steps d is joined in the solid-liquid separator, separate.Washery refuse is removed insolubles.Collect filtrate, filtrate behind membrane filtration, is made look liquid concentration C %=10～50%.
Wherein, employed acid binding agent, catalyzer, auxiliary agent and coloured light and intensity are adjusted agent and are that those of ordinary skills use always, those of ordinary skills as required, need not creative work can select its kind and consumption.
Yet, preferably,
Employed acid binding agent is a sodium bicarbonate among the described step b.
Catalyst system therefor is a pyridine derivate.
Adjuvant used is in sodium-chlor, Repone K, Sodium sulfate anhydrous.min(99), the glucose one or more.
Employed acid binding agent is 10～40% sodium hydroxide solutions in the described steps d.
Carry out the adjustment of intensity with glucose and Sodium sulfate anhydrous.min(99) among the described step e.
The invention has the beneficial effects as follows: the resulting hair of the present invention has higher reactivity with blue active dye, and good solubleness has very bright-coloured beautiful coloured light; The light fastness performance is fabulous, has very high exhaustion rate and degree of fixation.The preceding assembly of adding after auxiliary agent and film are handled mixes technology, and the generation that can stop waste water and waste residue has played very big promoter action to environment protection.
Description of drawings
Fig. 1 is the preparation technology schema of hair of the present invention with blue active dye.
Embodiment 1
1, allocation sheet:
Material name molecular weight mol ratio is rolled over hundred consumptions (Kg) charging capacitys (kilomol)
CuPc 576 1 341.3 0.5924
Chlorsulfonic acid 116.5 25.1 1732.4 0.5924
Sulfur oxychloride 119 8.4 592.2 0.5924
Monoethanolamine MEA BASF 61 2 73 0.5924
Oleum 98 151 8767.1 0.5924
Annotate: the oleum amount is converted with condenses dry product actual amount.
2, dyestuff preparation technology of the present invention operates as follows:
A, chlorosulfonation, ice are analysed
In the sulfonation jar, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc added in 2 hours consuming time. adjust 128 ℃ of temperature, 128～130 ℃ of holding temperatures were reacted 4 hours.Adjust 65～70 ℃ of temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 595 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.Adjust 90 ℃ of temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.Adjust 105 ℃ of temperature.105～110 ℃ of holding temperatures were reacted 1 hour.
Adjust 20～25 ℃ of temperature, the chlorosulphonation feed liquid of gained is joined ice with thread analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.Holding temperature-5～5 ℃ stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To filtrate pH ≈ 3, remove spent acid with temperature-5～5 ℃ cold water washing filter cake.Collect filter cake.Filtrate is deposited in the spent acid storage tank.
B, condensation reaction
Add the chlorosulphonation filter cake in the condensation jar, be diluted with water to 6000 liters, pulled an oar 30 minutes, will be diluted with water to concentration then is 20%, stirs down, with 73 kilograms of addings of Monoethanolamine MEA BASF, then pyridine catalyst is added.Adjust 28 ℃ of temperature.Add 96% yellow soda ash, adjust pH=8.0～8.5,28～30 ℃ of holding temperatures are kept pH=8.0～8.5, react 12 hours.The condensated liquid volume is 6500 liters, 12% adding sodium-chlor by volume.Stir, add solid-liquid separator.Filter cake is dried, and gets 830 kilograms of condenses dry products.
C, esterification, ice are analysed
102.8% oleum that in the esterification jar, adds 8300 kilograms, the circulating water cooling.830 kilograms of condenses dry products are joined in 102.8% oleum.10～20 ℃ of controlled temperature added the condenses dry product in 2 hours consuming time.Adjust 40 ℃ of temperature.Holding temperature was reacted 5 hours.
Adjust 20～25 ℃ of temperature, follow the trash ice thread to join ice the carboxylate feed liquid of gained and analyse in the jar.0～5 ℃ of controlled temperature added the carboxylate feed liquid in 2 hours consuming time.0～5 ℃ of holding temperature stirred 1 hour.
D, alkaline purification reaction
With the look liquid of gained, adjust 6～8 ℃ of temperature, add 40% sodium hydroxide solution and adjust pH=11.5～12.5,5～10 ℃ of holding temperatures are kept pH=11.5～12.5, react 1 hour.Adjust pH=6.0～6.5 with 30% hydrochloric acid.
E, removal insolubles
Add 20 kilograms in diatomite, stir.Look liquid is joined in the solid-liquid separator, separate.Washery refuse is removed insolubles.Collect filtrate, filtrate behind membrane filtration, is made look liquid concentration C %=30%.
The adjustment of f, coloured light and intensity
Look liquid with small-sized spray tower drying, is dyeed.Carry out the adjustment of coloured light and intensity again according to coloration result.
G, drying
Look liquid is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying, obtain hair blue active dye finished product with 95～100 ℃ temperature outs.
H, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.530 kilograms of this 0.5924 mole of gained, 100% dyestuffs.
Preparation hair blue active dye norm quota of consumption table of the present invention:
| Material name | Unit consumption, Kg/T |
| CuPc | 660.3 |
| Chlorsulfonic acid | 3301.5 |
| Sulfur oxychloride | 1122.5 |
| Monoethanolamine MEA BASF | 137.7 |
| Oleum | 15660 |
| Yellow soda ash | 3020 |
| Sodium hydroxide | 570 |
| Hydrochloric acid | 950 |
| Sodium-chlor | 1480 |
Preparation hair blue active dye application performance table of the present invention
Embodiment 2
Dyestuff preparation technology of the present invention operates as follows:
A, chlorosulfonation, ice are analysed
In the sulfonation jar, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc added in 2 hours consuming time. adjust 128 ℃ of temperature, 128～130 ℃ of holding temperatures were reacted 4 hours.Adjust 65～70 ℃ of temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 595 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.Adjust 90 ℃ of temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.Adjust 105 ℃ of temperature.105～110 ℃ of holding temperatures were reacted 1 hour.
Adjust 20～25 ℃ of temperature, the chlorosulphonation feed liquid of gained is joined ice with thread analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.Holding temperature-5～5 ℃ stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To filtrate pH ≈ 3, remove spent acid with temperature-5～5 ℃ cold water washing filter cake.Collect filter cake.Filtrate is deposited in the spent acid storage tank.
B, condensation reaction
Add the chlorosulphonation filter cake in the condensation jar, be diluted with water to 6000 liters, pulled an oar 30 minutes, will be diluted with water to concentration then is 20%, stirs down, with 73 kilograms of addings of Monoethanolamine MEA BASF, then pyridine catalyst is added.Adjust 28 ℃ of temperature.Add 96% yellow soda ash, adjust pH=7.0～7.5,28～30 ℃ of holding temperatures are kept pH=7.0～7.5, react 8 hours.The condensated liquid volume is 6500 liters, 15% adding sodium-chlor by volume.Stir, add solid-liquid separator.Filter cake is dried, and gets 831 kilograms of condenses dry products.
C, esterification, ice are analysed
102.8% oleum that in the esterification jar, adds 8310 kilograms, the circulating water cooling.831 kilograms of condenses dry products are joined in 102.8% oleum.10～20 ℃ of controlled temperature added the condenses dry product in 2 hours consuming time.Adjust 40 ℃ of temperature.Holding temperature was reacted 5 hours.
Adjust 20～25 ℃ of temperature, follow the trash ice thread to join ice the carboxylate feed liquid of gained and analyse in the jar.0～5 ℃ of controlled temperature added the carboxylate feed liquid in 2 hours consuming time.0～5 ℃ of holding temperature stirred 1 hour.
D, alkaline purification reaction
With the look liquid of gained, adjust 6～8 ℃ of temperature, add 40% sodium hydroxide solution and adjust pH=11.5～12.5,5～10 ℃ of holding temperatures are kept pH=11.5～12.5, react 1 hour.Adjust pH=6.0～6.5 with 30% hydrochloric acid.
E, removal insolubles
Add 20 kilograms in diatomite, stir.Look liquid is joined in the solid-liquid separator, separate.Washery refuse is removed insolubles.Collect filtrate, filtrate behind membrane filtration, is made look liquid concentration C %=30%.
The adjustment of f, coloured light and intensity
Look liquid with small-sized spray tower drying, is dyeed.Carry out the adjustment of coloured light and intensity again according to coloration result.
G, drying
Look liquid is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying, obtain hair blue active dye finished product with 95～100 ℃ temperature outs.
H, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.500 kilograms of this 0.5924 mole of gained, 100% dyestuffs.
Embodiment 3
Dyestuff preparation technology of the present invention operates as follows:
A, chlorosulfonation, ice are analysed
In the sulfonation jar, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc added in 2 hours consuming time. adjust 128 ℃ of temperature, 128～130 ℃ of holding temperatures were reacted 4 hours.Adjust 65～70 ℃ of temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 595 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.Adjust 90 ℃ of temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.Adjust 105 ℃ of temperature.105～110 ℃ of holding temperatures were reacted 1 hour.
Adjust 20～25 ℃ of temperature, the chlorosulphonation feed liquid of gained is joined ice with thread analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.Holding temperature-5～5 ℃ stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To filtrate pH ≈ 3, remove spent acid with temperature-5～5 ℃ cold water washing filter cake.Collect filter cake.Filtrate is deposited in the spent acid storage tank.
B, condensation reaction
Add the chlorosulphonation filter cake in the condensation jar, be diluted with water to 6000 liters, pulled an oar 30 minutes, will be diluted with water to concentration then is 20%, stirs down, with 73 kilograms of addings of Monoethanolamine MEA BASF, then pyridine catalyst is added.Adjust 28 ℃ of temperature.Add 96% yellow soda ash, adjust pH=11.0～11.5,28～30 ℃ of holding temperatures are kept pH=11.0～11.5, react 24 hours.The condensated liquid volume is 6500 liters, 8% adding sodium-chlor by volume.Stir, add solid-liquid separator.Filter cake is dried, and gets 829 kilograms of condenses dry products.
C, esterification, ice are analysed
102.8% oleum that in the esterification jar, adds 8290 kilograms, the circulating water cooling.829 kilograms of condenses dry products are joined in 102.8% oleum.10～20 ℃ of controlled temperature added the condenses dry product in 2 hours consuming time.Adjust 40 ℃ of temperature.Holding temperature was reacted 5 hours.
Adjust 20～25 ℃ of temperature, follow the trash ice thread to join ice the carboxylate feed liquid of gained and analyse in the jar.0～5 ℃ of controlled temperature added the carboxylate feed liquid in 2 hours consuming time.0～5 ℃ of holding temperature stirred 1 hour.
D, alkaline purification reaction
With the look liquid of gained, adjust 6～8 ℃ of temperature, add 40% sodium hydroxide solution and adjust pH=11.5～12.5,5～10 ℃ of holding temperatures are kept pH=11.5～12.5, react 1 hour.Adjust pH=6.0～6.5 with 30% hydrochloric acid.
E, removal insolubles
Add 20 kilograms in diatomite, stir.Look liquid is joined in the solid-liquid separator, separate.Washery refuse is removed insolubles.Collect filtrate, filtrate behind membrane filtration, is made look liquid concentration C %=30%.
The adjustment of f, coloured light and intensity
Look liquid with small-sized spray tower drying, is dyeed.Carry out the adjustment of coloured light and intensity again according to coloration result.
G, drying
Look liquid is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying, obtain hair blue active dye finished product with 95～100 ℃ temperature outs.
H, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.540 kilograms of this 0.5924 mole of gained, 100% dyestuffs.
Embodiment 4
1, allocation sheet:
Material name molecular weight mol ratio is rolled over hundred consumptions (Kg) charging capacitys (kilomol)
CuPc 576 1 341.3 0.5924
Chlorsulfonic acid 116.5 25.1 1732.4 0.5924
Sulfur oxychloride 119 8.4 592.2 0.5924
Monoethanolamine MEA BASF 61 1.5 54.8 0.5924
Oleum 98 149 8650.5 0.5924
Annotate: the oleum amount is converted with condenses dry product actual amount.
2, dyestuff preparation technology of the present invention operates as follows:
A, chlorosulfonation, ice are analysed
In the sulfonation jar, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc added in 2 hours consuming time. adjust 128 ℃ of temperature, 128～130 ℃ of holding temperatures were reacted 4 hours.Adjust 65～70 ℃ of temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 595 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.Adjust 90 ℃ of temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.Adjust 105 ℃ of temperature.105～110 ℃ of holding temperatures were reacted 1 hour.
Adjust 20～25 ℃ of temperature, the chlorosulphonation feed liquid of gained is joined ice with thread analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.Holding temperature-5～5 ℃ stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To filtrate pH ≈ 3, remove spent acid with temperature-5～5 ℃ cold water washing filter cake.Collect filter cake.Filtrate is deposited in the spent acid storage tank.
B, condensation reaction
Add the chlorosulphonation filter cake in the condensation jar, be diluted with water to 6000 liters, pulled an oar 30 minutes, will be diluted with water to concentration then is 20%, stirs down, with 54.8 kilograms of addings of Monoethanolamine MEA BASF, then pyridine catalyst is added.Adjust 28 ℃ of temperature.Add 96% yellow soda ash, adjust pH=8～8.5,28～30 ℃ of holding temperatures are kept pH=8～9.0, react 12 hours.The condensated liquid volume is 6500 liters, 15% adding sodium-chlor by volume.Stir, add solid-liquid separator.Filter cake is dried, and gets 840 kilograms of condenses dry products.
C, esterification, ice are analysed
102.8% oleum that in the esterification jar, adds 8400 kilograms, the circulating water cooling.840 kilograms of condenses dry products are joined in 102.8% oleum.10～20 ℃ of controlled temperature added the condenses dry product in 2 hours consuming time.Adjust 40 ℃ of temperature.43～45 ℃ of holding temperatures were reacted 5 hours.
Adjust 20～25 ℃ of temperature, follow the trash ice thread to join ice the carboxylate feed liquid of gained and analyse in the jar.0～5 ℃ of controlled temperature added the carboxylate feed liquid in 2 hours consuming time.0～5 ℃ of holding temperature stirred 1 hour.
D, alkaline purification reaction
With the look liquid of gained, adjust 6～8 ℃ of temperature, add 40% sodium hydroxide solution and adjust pH=11.5～12.5,5～10 ℃ of holding temperatures are kept pH=11.5～12.5, react 1 hour.Adjust pH=6.0～6.5 with 30% hydrochloric acid.
E, removal insolubles
Add 20 kilograms in diatomite, stir.Look liquid is joined in the solid-liquid separator, separate.Washery refuse is removed insolubles.Collect filtrate, filtrate behind membrane filtration, is made look liquid concentration C %=30%.
The adjustment of f, coloured light and intensity
Look liquid with small-sized spray tower drying, is dyeed.Carry out the adjustment of coloured light and intensity again according to coloration result.
G, drying
Look liquid is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying, obtain hair blue active dye finished product with 95～100 ℃ temperature outs.
H, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.525 kilograms of this 0.5924 mole of gained, 100% dyestuffs.
Embodiment 5
1, allocation sheet:
Material name molecular weight mol ratio is rolled over hundred consumptions (Kg) charging capacitys (kilomol)
CuPc 576 1 341.3 0.5924
Chlorsulfonic acid 116.5 25.1 1732.4 0.5924
Sulfur oxychloride 119 8.4 592.2 0.5924
Monoethanolamine MEA BASF 61 3 109.5 0.5924
Oleum 98 144.6 8394.7 0.5924
Annotate: the oleum amount is converted with condenses dry product actual amount.
2, dyestuff preparation technology of the present invention operates as follows:
A, chlorosulfonation, ice are analysed
In the sulfonation jar, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc added in 2 hours consuming time. adjust 128 ℃ of temperature, 128～130 ℃ of holding temperatures were reacted 4 hours.Adjust 65～70 ℃ of temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 595 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.Adjust 90 ℃ of temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.Adjust 105 ℃ of temperature.105～110 ℃ of holding temperatures were reacted 1 hour.
Adjust 20～25 ℃ of temperature, the chlorosulphonation feed liquid of gained is joined ice with thread analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.Holding temperature-5～5 ℃ stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To filtrate pH ≈ 3, remove spent acid with temperature-5～5 ℃ cold water washing filter cake.Collect filter cake.Filtrate is deposited in the spent acid storage tank.
B, condensation reaction
Add the chlorosulphonation filter cake in the condensation jar, be diluted with water to 6000 liters, pulled an oar 30 minutes, will be diluted with water to concentration then is 20%, stirs down, with 73 kilograms of addings of Monoethanolamine MEA BASF, then pyridine catalyst is added.Adjust 28 ℃ of temperature.Add 96% yellow soda ash, adjust pH=8～8.5,28～30 ℃ of holding temperatures are kept pH=8～9.0, react 12 hours.The condensated liquid volume is 6500 liters, 12% adding sodium-chlor by volume.Stir, add solid-liquid separator.Filter cake is dried, and gets 815 kilograms of condenses dry products.
C, esterification, ice are analysed
102.8% oleum that in the esterification jar, adds 8150 kilograms, the circulating water cooling.815 kilograms of condenses dry products are joined in 102.8% oleum.10～20 ℃ of controlled temperature added the condenses dry product in 2 hours consuming time.Adjust 40 ℃ of temperature.Holding temperature was reacted 5 hours.
Adjust 20～25 ℃ of temperature, follow the trash ice thread to join ice the carboxylate feed liquid of gained and analyse in the jar.0～5 ℃ of controlled temperature added the carboxylate feed liquid in 2 hours consuming time.0～5 ℃ of holding temperature stirred 1 hour.
D, alkaline purification reaction
With the look liquid of gained, adjust 6～8 ℃ of temperature, add 40% sodium hydroxide solution and adjust pH=11.5～12.5,5～10 ℃ of holding temperatures are kept pH=11.5～12.5, react 1 hour.Adjust pH=6.0～6.5 with 30% hydrochloric acid.
E, removal insolubles
Add 20 kilograms in diatomite, stir.Look liquid is joined in the solid-liquid separator, separate.Washery refuse is removed insolubles.Collect filtrate, filtrate behind membrane filtration, is made look liquid concentration C %=30%.
The adjustment of f, coloured light and intensity
Look liquid with small-sized spray tower drying, is dyeed.Carry out the adjustment of coloured light and intensity again according to coloration result.
G, drying
Look liquid is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying, obtain hair blue active dye finished product with 95～100 ℃ temperature outs.
H, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.537 kilograms of this 0.5924 mole of gained, 100% dyestuffs.
Embodiment 6
Dyestuff preparation technology of the present invention operates as follows:
A, chlorosulfonation, ice are analysed
In the sulfonation jar, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc added in 2 hours consuming time. adjust 128 ℃ of temperature, 128～130 ℃ of holding temperatures were reacted 4 hours.Adjust 65～70 ℃ of temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 595 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.Adjust 90 ℃ of temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.Adjust 105 ℃ of temperature.105～110 ℃ of holding temperatures were reacted 1 hour.
Adjust 20～25 ℃ of temperature, the chlorosulphonation feed liquid of gained is joined ice with thread analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.Holding temperature-5～5 ℃ stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To filtrate pH ≈ 3, remove spent acid with temperature-5～5 ℃ cold water washing filter cake.Collect filter cake.Filtrate is deposited in the spent acid storage tank.
B, condensation reaction
Add the chlorosulphonation filter cake in the condensation jar, be diluted with water to 6000 liters, pulled an oar 30 minutes, will be diluted with water to concentration then is 20%, stirs down, with 73 kilograms of addings of Monoethanolamine MEA BASF, then pyridine catalyst is added.Adjust 28 ℃ of temperature.Add 96% yellow soda ash, adjust pH=8～8.5,28～30 ℃ of holding temperatures are kept pH=8～9.0, react 12 hours.The condensated liquid volume is 6500 liters, 12% adding sodium-chlor by volume.Stir, add solid-liquid separator.Filter cake is dried, and gets 830 kilograms of condenses dry products.
C, esterification, ice are analysed
102.8% oleum that in the esterification jar, adds 8300 kilograms, the circulating water cooling.830 kilograms of condenses dry products are joined in 102.8% oleum.10～20 ℃ of controlled temperature added the condenses dry product in 2 hours consuming time.Adjust 40 ℃ of temperature.Holding temperature was reacted 5 hours.
Adjust 20～25 ℃ of temperature, follow the trash ice thread to join ice the carboxylate feed liquid of gained and analyse in the jar.0～5 ℃ of controlled temperature added the carboxylate feed liquid in 2 hours consuming time.0～5 ℃ of holding temperature stirred 1 hour.
With the look liquid of gained, adjust 6～8 ℃ of temperature, add 40% sodium hydroxide solution and adjust pH=6.0～6.5.
D, removal insolubles
With the look liquid of gained, adjust 6～8 ℃ of temperature, add 40% sodium hydroxide solution and adjust pH=6.0～6.5.Add 20 kilograms in diatomite, stir.Look liquid is joined in the solid-liquid separator, separate.Washery refuse is removed insolubles.Collect filtrate, filtrate behind membrane filtration, is made look liquid concentration C %=30%.
The adjustment of e, coloured light and intensity
Look liquid with small-sized spray tower drying, is dyeed.Carry out the adjustment of coloured light and intensity again according to coloration result.
F, drying
Look liquid is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying, obtain hair blue active dye finished product with 95～100 ℃ temperature outs.
G, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.515 kilograms of this 0.5924 mole of gained, 100% dyestuffs.
Embodiment 7
1, allocation sheet:
Material name molecular weight mol ratio is rolled over hundred consumptions (Kg) charging capacitys (kilomol)
CuPc 576 1 341.3 0.5924
Chlorsulfonic acid 116.5 25.1 1732.4 0.5924
Sulfur oxychloride 119 8.4 592.2 0.5924
Nicotinic acid 123 2 145.8 0.5924
Annotate: the oleum amount is converted with condenses dry product actual amount.
2, dyestuff preparation technology of the present invention operates as follows:
A, chlorosulfonation, ice are analysed
In the sulfonation jar, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc added in 2 hours consuming time. adjust 128 ℃ of temperature, 128～130 ℃ of holding temperatures were reacted 4 hours.Adjust 65～70 ℃ of temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 595 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.Adjust 90 ℃ of temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.Adjust 105 ℃ of temperature.105～110 ℃ of holding temperatures were reacted 1 hour.
Adjust 20～25 ℃ of temperature, the chlorosulphonation feed liquid of gained is joined ice with thread analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.Holding temperature-5～5 ℃ stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To filtrate pH ≈ 3, remove spent acid with temperature-5～5 ℃ cold water washing filter cake.Collect filter cake.Filtrate is deposited in the spent acid storage tank.
B, condensation reaction
Add the chlorosulphonation filter cake in the condensation jar, be diluted with water to 6000 liters, pulled an oar 30 minutes, will be diluted with water to concentration then is 20%, stirs down, with 145.8 kilograms of addings of nicotinic acid.Adjust 28 ℃ of temperature.Add 96% yellow soda ash, adjust pH=8～8.5,28～30 ℃ of holding temperatures are kept pH=8～9.0, react 12 hours.The condensated liquid volume is 6500 liters.
C, removal insolubles
Add 20 kilograms in diatomite, stir.Look liquid is joined in the solid-liquid separator, separate.Washery refuse is removed insolubles.Collect filtrate, filtrate behind membrane filtration, is made look liquid concentration C %=30%.
The adjustment of d, coloured light and intensity
Look liquid with small-sized spray tower drying, is dyeed.Carry out the adjustment of coloured light and intensity again according to coloration result.
E, drying
Look liquid is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying, obtain hair blue active dye finished product with 95～100 ℃ temperature outs.
F, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Warehouse-in is deposited.480 kilograms of this 0.5924 mole of gained, 100% dyestuffs.
1,2,3 of examples add Monoethanolamine MEA BASF and are 73 kilograms, and condensation condition is different.After testing, example 2 must be measured minimum, and example 1,3 must be measured approaching.Compare with the standard of being formulated in the test, example 1 is the most approaching; Example 2 floats, and example 3 is darker, but all bigger with standard difference, and poor performance.
4,5 of examples add Monoethanolamine MEA BASF and are respectively 54.8 public affairs, 109.5 kilograms, and after testing, example 4,5 must be measured with example 1 and almost maintain an equal level.Compare with the standard of being formulated in the test, example 5 maintains an equal level with example 1, and example 4 is slightly poor.
Example 6 reduces step alkaline purification reaction than example 1, must measure to be less than example 1, and the equal sample of being formulated with experiment of table compares, and example 6 is darker, and poor performance.
Example 7 to add nicotinic acid be 145.8 kilograms, after testing, must measure and be less than example 1.The equal sample of being formulated with experiment of table compares, and example 7 is darker, and poor performance.
Because the present invention adopts membrane technology, to saltout, dry technology than tradition and save a large amount of energy, wastewater discharge also has obvious minimizing, and saltiness and COD value also decline to a great extent in the waste water.
Because the present invention adopts spraying drying, to dry resulting dyestuff crystal formation different with present technology, so the hair of preparation method of the present invention preparation is big with the solubleness of blue active dye, coloured light is bright, favorable reproducibility, to colour purity just.
Below in conjunction with the embodiments the present invention is described in more detail; yet; should be understood that; without prejudice to the prerequisite that breaks away from spirit of the present invention under; those of ordinary skills can make various changes or change to the present invention, and these changes or change fall within protection scope of the present invention equally.Protection scope of the present invention is determined with the content and the equivalent thereof of appended claim.
Claims (24)
1. a hair blue active dye is characterized in that, has following general structure wherein:
3.5≤X+Y≤4
M represents basic metal, is preferably sodium or potassium, more preferably sodium;
R＝—NH-R
3 —NH-R
2OSO
3M
In a kind of;
Among the R,
R
1Identical or different, and expression C
1-6Alkyl;
R
2Identical or different, and expression C
1-6Alkyl, ethyl more preferably;
R
3Identical or different, and expression C
2-4Thiazolinyl;
X
1Identical or different, and expression halogen, preferably each X
1Identical and the expression bromine.
2, hair according to claim 1 is used blue active dye, wherein:
R
1Identical or different and the expression C
1-4Alkyl,
R
2Identical or different and the expression C
1-4Alkyl,
R
3Identical or different and the expression vinyl,
X
1The expression bromine.
3, hair according to claim 1 and 2 is used blue active dye, wherein:
R
1Be methyl, R
2Be ethyl.
4, hair according to claim 3 is used blue active dye, and wherein, M is a sodium, each R
1Identical and be methyl; Each R
2Identical and be ethyl; Each R
3Identical and be vinyl; Each X
1Identical and the expression bromine.
5, the described hair of one of a kind of claim 1-4 comprises the steps: with the preparation method of blue active dye
A. CuPc and chlorsulfonic acid are carried out chlorosulfonation, crystallisation by cooling separates then, obtains CuPc chlorosulphonation thing;
B. condensation reaction: with the mass percent concentration of solution is chlorosulphonation thing and Monoethanolamine MEA BASF 5-40%, that a step obtains, and catalyzer and acid binding agent mix, and in pH=1.0～12.0,10-80 ℃ was reacted 8-16 hour down; The auxiliary agent that adds 1-25% (volume) again stirs and carries out solid-liquid separation, and oven dry obtains dry condensed products.
C. esterification: the condensed products of step b gained through esterification, is cooled off, Crystallization Separation then, make carboxylate;
D. alkaline purification reaction: in the carboxylate feed liquid of step c gained, add acid binding agent, and pH=11.0～13.0 ,-10～40 ℃, reacted 0.5-2 hour; Then, pH is adjusted to 5.0-8.0, obtains look liquid; This look liquid is hair blue dyes of the present invention.
6, method according to claim 5, wherein in step a, crystallisation by cooling adopts ice to analyse, and separates and adopts solid-liquid separator to finish.
7, according to claim 5 or 6 described methods, wherein in step b, first-selected Monoethanolamine MEA BASF and the catalyzer of adding adjusted 10～80 ℃ of temperature; Add acid binding agent, and in pH=1.0～12.0 time, reacted 12 hours.
8, according to the described method of one of claim 5-7, wherein in step c, adopt the oleum of 98-120% to carry out esterification, the esterification condition is :-10 ℃ to 100 ℃, the reaction times is 5-8 hour; Cooling, Crystallization Separation is :-10 ℃ to 40 ℃, stir and carried out solid-liquid separation 2-4 hour.
9, according to the described method of one of claim 5-8, wherein in steps d, the alkaline purification reaction times is 1 hour, adopt mineral acid with pH regulator to 5.0-8.0.
10, method according to claim 9 adopts 30% salt acid for adjusting pH value.
11,, also comprise step e in addition according to the described method of one of claim 5-10:
E. remove insolubles: in the look liquid of steps d gained, add diatomite, and carry out solid-liquid separation; Make filtrate then behind membrane filtration, obtain the look liquid of C%=10-50%.
12, method according to claim 11 wherein, is separated in solid-liquid separator, and after the separation, washery refuse is removed insolubles, collects filtrate, and filtrate is carried out membrane filtration, makes look liquid concentration C %=10～50%.
13, according to claim 11 or 12 described methods, also can comprise step f in addition:
F. piece together before and mix: the look liquid to step e gained carries out spraying drying, and dyeing is carried out coloured light and intensity adjustment according to coloration result again.
14, method according to claim 13, wherein, with small-sized spray tower drying, the adjustment of coloured light and intensity is carried out in dyeing again according to coloration result with the look liquid of step e gained; Wherein, use glucose and/or Sodium sulfate anhydrous.min(99) to carry out the intensity adjustment.
15, according to the described method of one of claim 11-14, also comprise the steps g:
G. dry: the look liquid to step e gained carries out spraying drying, to obtain hair blue active dye product.
16, method according to claim 15 wherein, joins the look liquid of step e gained in the feed liquid preheater, adjusts 210 ℃ of inlet temperatures, and 90～100 ℃ of temperature outs are carried out spraying drying, to obtain hair blue active dye product.
According to the described method of one of claim 5-16, it is characterized in that 17, described step a is: in chlorsulfonic acid, add CuPc, stir.0～100 ℃ of controlled temperature, 100～140 ℃ of temperature were adjusted in the CuPc adding, reacted 2 hours in 1～2 hour consuming time, 10～80 ℃ of holding temperatures, 10～80 ℃ of holding temperatures were reacted 2 hours with the sulfur oxychloride adding in 1～2 hour consuming time, 80～100 ℃ of holding temperatures, reacted 1 hour, 100～130 ℃ of holding temperatures were reacted 1 hour;
Adjust 0～100 ℃ of temperature, follow trash ice to join ice resulting chlorosulphonation feed liquid and analyse in the jar, controlled temperature-10～40 ℃; 1～2 hour consuming time, the chlorosulphonation feed liquid is added; Holding temperature-10～40 ℃ stirred 1 hour; Ice is analysed liquid join in the solid-liquid separator, separate; With temperature-10～40 ℃ water washing filter cake, remove spent acid, collect filter cake.
According to the described method of one of claim 5-17, it is characterized in that 18, described step b is: with the prepared chlorosulphonation thing of step a filter cake thin up, the mass percent concentration that makes solution is 5～40%; Stir down,, add catalyzer simultaneously the disposable adding of Monoethanolamine MEA BASF; Adjust 10～80 ℃ of temperature, add acid binding agent, adjust pH=1.0～12.0,10～80 ℃ of holding temperatures were reacted 12 hours, and 1～25% adding auxiliary agent by volume, stirred, and joined in the solid-liquid separator, separated; Collect filter cake.
According to the described method of claim 5-18, it is characterized in that 19, described step c is: the prepared dry product of step b is joined in 98～120% oleums, controlled temperature-10～20 ℃, 20～100 ℃ of holding temperatures were reacted 5 hours with the dry product adding in 1～2 hour consuming time;
Adjust 0～40 ℃ of temperature, follow trash ice to join ice the carboxylate feed liquid of gained and analyse in the jar, controlled temperature-10～40 ℃ added the carboxylate feed liquid in 1～2 hour consuming time, and holding temperature-10～40 ℃ stirred 1 hour.
According to the described method of one of claim 5-19, it is characterized in that 20, described steps d is: with the carboxylate feed liquid of step c gained, adjust temperature-10～40 ℃, add acid binding agent and adjust pH=11.0～13.0, holding temperature-10～40 ℃, keep pH=11.0～13.0, reacted 1 hour; Adjust pH=5.0～8.0 with 30%HCl.
According to the described method of one of claim 5-20, it is characterized in that 21, described step e is: the resulting look liquid of steps d is joined in the solid-liquid separator, separate, washery refuse is removed insolubles; Collect filtrate, filtrate behind membrane filtration, is made look liquid concentration C %=10～50%.
22, according to the described method of one of claim 5-21, it is characterized in that, employed acid binding agent is a sodium bicarbonate among the described step b, and catalyst system therefor is a pyridine derivate, and adjuvant used is in sodium-chlor, Repone K, Sodium sulfate anhydrous.min(99), the glucose one or more.
According to the described method of one of claim 5-22, it is characterized in that 23, employed acid binding agent is 10～40% sodium hydroxide solutions in the described steps d.
24, according to the described method of one of claim 5-23, it is characterized in that, carry out the adjustment of intensity with glucose and/or Sodium sulfate anhydrous.min(99) among the described step e.
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| CNA200810152920XA CN101418136A (en) | 2008-11-11 | 2008-11-11 | Blue reactive dyes for wool and preparation method thereof |
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| CN103333517B (en) * | 2013-06-27 | 2015-04-01 | 浙江劲光化工有限公司 | Turquoise blue water-soluble dye and preparation method thereof |
| CN104530746A (en) * | 2014-12-23 | 2015-04-22 | 浙江劲光化工有限公司 | Turquoise blue water-soluble dye and preparation method thereof |
| CN105295437A (en) * | 2015-12-02 | 2016-02-03 | 天津德凯化工股份有限公司 | Turquoise blue dye for inkjet printing and preparation method thereof |
| CN105331143A (en) * | 2015-12-02 | 2016-02-17 | 天津德凯化工股份有限公司 | Turquoise blue dye and preparing method thereof |
| CN105482496A (en) * | 2015-12-02 | 2016-04-13 | 天津德凯化工股份有限公司 | Turquoise blue dye for inkjet printing |
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Application publication date: 20090429 |