CN102391670A - Turquoise blue reactive dye as well as preparation method and application thereof - Google Patents
Turquoise blue reactive dye as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides turquoise blue reactive dye as well as a preparation method and application thereof. The dye has the following structure shown in the specification, wherein in the formula, x+y =3.5. The dye has small average particle diameter and low saltness; when in dyeing, the dye has gorgeous color, high coloring rate and good stability and repeatability; and the turquoise blue reactive dye is particularly suitable for inkjet printing, has excellent application performance and is convenient for use. Simultaneously, environment pollution can be reduced by the preparation and application of the dye, and the cost of the required raw material is low.
Description
Technical field
The present invention relates to a kind of chemically-reactive dyes, especially a kind of turquoise blue chemically-reactive dyes and preparation method thereof and the application in ink-jet printed.
Background technology
Ink-jet printed technology is exactly one of them main field, and this technology mainly contains two kinds: i.e. continous inkjet and drop on demand ink jet.These two kinds of printing techniques all have particular requirement to dyestuff in the ink or pigment dyestuff, like the purity of the pH value of the electric conductivity of the chemical structure of dyestuff, median size, the formation aqueous solution, dyestuff, the dyestuff content etc. of inorganic salt particularly.Development along with digital technique; Accurately control dyeing course with computingmachine, can enhance productivity and yield rate, reduce production costs; Reduce the pollution level of waste water to greatest extent; And present ink-jet is bigger with the dyestuff median size, and saltiness is high, dye uptake is low and fastness is low, can not satisfy ink-jet printed demand fully.
Summary of the invention
In order to solve the problems of the technologies described above, to the invention provides a kind of technical scheme and be: a kind of turquoise blue dyestuff has following general structure:
Wherein
X+y=3.5 in the formula, x＞0, y＞0;
R
1For:
A kind of in
.
Further R preferably
1For:
The preparation method of above-mentioned dyestuff, this method comprises the steps:
A, chlorosulfonation, ice are analysed
The cooling of adding chlorsulfonic acid circulating water after the reaction of adding CuPc, adds the sulfur oxychloride reaction again in enamel pot, gets the chlorosulphonation feed liquid; Adjust temperature once more, the chlorosulphonation feed liquid of gained is joined ice with thread analyse in the jar, controlled temperature stirs; Obtain ice and analyse liquid, ice is analysed liquid join in the solid-liquid separator, separate; The cold water washing filter cake is removed spent acid to the pH=7 that filtrates, and collects filter cake;
B, A substance dissolves
The A substance dissolves in water, is transferred pH=7 with 30% sodium hydroxide solution, material is dissolved entirely; Wherein the A material is a kind of in Sulphanilic Acid, m-sulfanilic acid, the ORTHO AMINO PHENOL SULPHONIC;
C, primary condensation
A step gained filter cake is joined in the b step gained solution, keep pH=7～8 with 30% sodium hydroxide solution, stirring reaction, reaction pH=7～8 are used the aluminium base silica gel thin-layer plate endpoint detection of TLC at last;
D, secondary condensation
With adding cyanuric chloride solution in the solution of B material, keep pH=2～3 with 10% yellow soda ash, stirring reaction, pH=2～4 are used the aluminium base silica gel thin-layer plate endpoint detection of TLC at last; Wherein the B material is an aniline-2,5-disulfonic acid, m-sulfanilic acid, Sulphanilic Acid, ORTHO AMINO PHENOL SULPHONIC, a kind of in β hydroxyethyl sulfone sulfate ester aniline, a β hydroxyethyl sulfone sulfate ester aniline, the adjacent β hydroxyethyl sulfone sulfate ester aniline;
E, three condensations
The solution of C material is added in the d step gained solution, behind the stirring reaction,, get three condensated liquids with the aluminium base silica gel thin-layer plate endpoint detection of TLC; The C material is 2, a kind of in 4-diamino benzene sulfonic acid sodium, ammoniacal liquor, the quadrol;
F, four condensations
C step gained solution is joined in three condensated liquids, keep pH=7～9 with 30% sodium hydroxide solution, stirring reaction is used the aluminium base silica gel thin-layer plate endpoint detection of TLC at last; Obtain the product of structural formula (I).
G, interpolation auxiliary agent
With sodium sulfate, mixed phosphate, one or more among Sodium hexametaphosphate 99, EDTA, the NNO join in the product solution of structural formula (I), stir, and are subsequent use;
H, removal insolubles
G step gained reaction solution is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank;
I, purification
With the feed liquid of collecting through membrane filtration, and with the concentration of the feed liquid percentage concentration 25% that improves the quality.One time membrane filtration waste water joins in the look liquid, continues membrane filtration.Secondary membrane filtration waste water as dyestuff at the bottom of water jacket use;
The adjustment of j, coloured light and intensity
From the reaction storage tank, extract feed liquid 200ml, dry and dyeing with small-sized spray drier; According to coloration result, add an amount of other batch dyestuff, carry out the coloured light adjustment, add glucose in proportion according to the UV intensity of dyestuff again and Sodium sulfate anhydrous.min(99) carries out the adjustment of intensity;
K, drying
The look liquid of j step is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying with 95～100 ℃ temperature outs.
Used raw material all is a disclosed known compound in the prior art in the aforesaid method, all can buy from market to obtain.
Chemically-reactive dyes of the present invention is suitable for multiple material is dyeed and stamp, and particularly hydroxyl or nitrogenous filamentary material comprise the cellulosic fibre material of paper, silk, leather, wool, tynex and urethane, particularly all kinds.Described filamentary material is a native cellulose fibre for example, like cotton, flax and hemp and Mierocrystalline cellulose and regenerated cellulose.Dyestuff of the present invention also is suitable for the hydroxyl fiber that exists in the BLENDED FABRIC is dyeed and stamp.
Reactive dye of the present invention is particluarly suitable for using ink jet printing method that fabric fiber material, paper or plastics film are printed dyeing or stamp; Dyestuff should have low saline salinity when being used for ink jet printing method; The dyestuff that has than supersalinity can carry out desalination like technology such as ultrafiltration, r-o-or dialysis and reach low saline salinity through for example membrane separation process.
The dyestuff product of resulting structures formula of the present invention (I), the average diameter grain is little, and saltiness is low; Beautiful in colour during dyeing, dye uptake is high, and is stable; Favorable reproducibility is particularly useful for using in the ink-jet cloth printing, and application performance is excellent; Easy to use, preparation of this dyestuff simultaneously and application can reduce environmental pollution, and the desired raw material cost is low.
Embodiment
Following embodiment just to the explanation of technical scheme of the present invention, does not form any restriction to technical scheme of the present invention and protection domain.
Embodiment 1
A, chlorosulfonation, ice are analysed
In enamel pot, add 1750 kilograms of chlorsulfonic acids, circulating water cooling, 40～50 ℃ of controlled temperature.CuPc being added in 2 hours consuming time. 128 ℃ of adjustment temperature, 128～130 ℃ of holding temperatures were reacted 4 hours.65 ℃ of adjustment temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 560 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.90 ℃ of adjustment temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.105 ℃ of adjustment temperature.105～110 ℃ of holding temperatures were reacted 1 hour.
20～25 ℃ of temperature of adjustment join ice with the chlorosulphonation feed liquid of gained with thread and 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 the pH ≈ 3 that filtrates, remove spent acid with temperature-5～5 ℃ cold water washing filter cake.Collect filter cake.Filtrating is deposited in the spent acid storage tank.
B, Sulphanilic Acid dissolving
In enamel pot, put into 1500 liters in end water, add Sulphanilic Acid 205.2Kg, transfer pH=7, material is dissolved entirely, clarification with 30% sodium hydroxide solution.Volume is 2000 liters, and the mass percent concentration of solution is 10%.
C, primary condensation
A step gained filter cake is joined in the Sulphanilic Acid solution adjustment temperature to 20 ℃.Keep pH=7～8 with 30% sodium hydroxide solution, stirring reaction 15～20 hours.20～25 ℃ of temperature of reaction, reaction pH=7～8.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
D, aniline-2, the dissolving of 5-disulfonic acid
In enamel pot, put into 1500 liters in end water, add aniline-2,5-disulfonic acid 225Kg transfers pH=9 with 30% sodium hydroxide solution, material is dissolved entirely, clarification.Volume is 2250 liters, and the mass percent concentration of solution is 10%.
E, secondary condensation
Put into 500 liters of frozen water in the phase reaction jar, add cyanuric chloride 167.2Kg, material is mixed.0～5 ℃ of controlled temperature, control pH=2～3 added b step solution in 45～60 minutes, kept pH=2～3 with 10% yellow soda ash then, stirring reaction 3 hours.0～5 ℃ of temperature of reaction, reaction pH=2～3.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
F, three condensations
With 2,4-diamino benzene sulfonic acid sodium 186.6Kg adds in the c solution, and insulated and stirred reaction 1 hour is warming up to 40 ℃, keeps pH=6～7 with 30% sodium hydroxide solution, stirring reaction 5 hours.40～45 ℃ of temperature of reaction, reaction pH=6～7.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
G, four condensations
Just c step gained condensated liquid joins in three condensated liquids, adjustment temperature to 35 ℃.Keep pH=8～9 with 30% sodium hydroxide solution, stirring reaction 10～15 hours.35～40 ℃ of temperature of reaction, reaction pH=8～9.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
H, interpolation auxiliary agent
With 50 kilograms sodium sulfate, mixed phosphate, one or more among Sodium hexametaphosphate 99, EDTA, the NNO join in the g step gained reaction solution, stir 15 minutes, and are subsequent use.
I, removal insolubles
H step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.3 the waste residue about kilogram is used for engineering soil.
J, purification
With the filtrating of collecting through membrane filtration, and with the concentration of the feed liquid percentage concentration 25% that improves the quality.One time membrane filtration waste water joins in the look liquid, continues membrane filtration.Secondary membrane filtration waste water as dyestuff at the bottom of water jacket use.
The adjustment of k, coloured light and intensity
From the reaction storage tank, extract feed liquid 200ml, dry and dyeing with small-sized spray drier.According to coloration result, add an amount of other batch dyestuff, carry out the coloured light adjustment.Add glucose in proportion according to the UV intensity of dyestuff again and Sodium sulfate anhydrous.min(99) carries out the adjustment of intensity.
L, drying
The look liquid of k step is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying with 95～100 ℃ temperature outs.
M, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Get formula turquoise blue dyestuff
Can the Sulphanilic Acid among the step b be replaced with ORTHO AMINO PHENOL SULPHONIC in addition, get formula turquoise blue dyestuff:
Sulphanilic Acid among the step b is replaced with m-sulfanilic acid, gets formula turquoise blue dyestuff:
Embodiment 2
A, chlorosulfonation, ice are analysed
In enamel pot, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc being added in 2 hours consuming time. 128 ℃ of adjustment temperature, 128～130 ℃ of holding temperatures were reacted 4 hours.60 ℃ of adjustment temperature, 60～65 ℃ of holding temperatures, 1.5 hours consuming time with 525 kilograms of addings of sulfur oxychloride.60～65 ℃ of holding temperatures were reacted 2 hours.90 ℃ of adjustment temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.100 ℃ of adjustment temperature.100～105 ℃ of holding temperatures were reacted 2 hours.
25～30 ℃ of temperature of adjustment join ice with the chlorosulphonation feed liquid of gained with thread and analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.0～5 ℃ of holding temperature stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To the pH ≈ 3 that filtrates, remove spent acid with 0～5 ℃ of cold water washing filter cake of temperature.Collect filter cake.Filtrating is deposited in the spent acid storage tank.
B, Sulphanilic Acid dissolving
In enamel pot, put into 975 liters in end water, add Sulphanilic Acid 133.38Kg, transfer pH=7, material is dissolved entirely, clarification with 30% sodium hydroxide solution.Volume is 1300 liters, and the mass percent concentration of solution is 10%.
C, primary condensation
A step gained filter cake is joined in the Sulphanilic Acid solution adjustment temperature to 20 ℃.Keep pH=7～8 with 30% sodium hydroxide solution, stirring reaction 15～20 hours.20～25 ℃ of temperature of reaction, reaction pH=7～8.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
D, aniline-2, the dissolving of 5-disulfonic acid
In enamel pot, put into 2000 liters in end water, add aniline-2,5-disulfonic acid 329.8Kg transfers pH=9 with 30% sodium hydroxide solution, material is dissolved entirely, clarification.Volume is 2750 liters, and the mass percent concentration of solution is 12%.
E, secondary condensation
Put into 1000 liters of frozen water in the phase reaction jar, add cyanuric chloride 250Kg, material is mixed.0～5 ℃ of controlled temperature, control pH=3～4 added b step solution in 45～60 minutes, kept pH=3～4 with 10% yellow soda ash then, stirring reaction 5 hours.0～5 ℃ of temperature of reaction, reaction pH=3～4.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
F, three condensations
Ammoniacal liquor 89Kg with 25% adds in the c solution, and insulated and stirred reaction 1 hour is warming up to 40 ℃, keeps pH=9～10 with 30% sodium hydroxide solution, stirring reaction 7 hours.40～45 ℃ of temperature of reaction, reaction pH=9～10.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
G, four condensations
C step gained condensated liquid is joined in three condensated liquids adjustment temperature to 35 ℃.Keep pH=7～8 with 30% sodium hydroxide solution, stirring reaction 15～20 hours.35～40 ℃ of temperature of reaction, reaction pH=7～8.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
H, interpolation auxiliary agent
With 50 kilograms sodium sulfate, mixed phosphate, one or more among Sodium hexametaphosphate 99, EDTA, the NNO join in the g step gained reaction solution, stir 15 minutes, and are subsequent use.
I, removal insolubles
H step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.3 the waste residue about kilogram is used for engineering soil.
J, purification
With the filtrating of collecting through membrane filtration, and with the concentration of the feed liquid percentage concentration 25% that improves the quality.One time membrane filtration waste water joins in the look liquid, continues membrane filtration.Secondary membrane filtration waste water as dyestuff at the bottom of water jacket use.
The adjustment of k, coloured light and intensity
From the reaction storage tank, extract feed liquid 200ml, dry and dyeing with small-sized spray drier.According to coloration result, add an amount of other batch dyestuff, carry out the coloured light adjustment.Add glucose in proportion according to the UV intensity of dyestuff again and Sodium sulfate anhydrous.min(99) carries out the adjustment of intensity.
L, drying
The look liquid of k step is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying with 95～100 ℃ temperature outs.
M, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Get formula turquoise blue dyestuff
Can the Sulphanilic Acid among the step b be replaced with ORTHO AMINO PHENOL SULPHONIC or m-sulfanilic acid in addition.
When replacing with ORTHO AMINO PHENOL SULPHONIC, get formula turquoise blue dyestuff:
When replacing with m-sulfanilic acid, get formula turquoise blue dyestuff:
Embodiment 3
A, chlorosulfonation, ice are analysed
In enamel pot, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc being added in 2 hours consuming time. 120 ℃ of adjustment temperature, 120～125 ℃ of holding temperatures were reacted 4 hours.65 ℃ of adjustment temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 490 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.90 ℃ of adjustment temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.105 ℃ of adjustment temperature.105～110 ℃ of holding temperatures were reacted 2 hours.
10～15 ℃ of temperature of adjustment join ice with the chlorosulphonation feed liquid of gained with thread and analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.5～15 ℃ of holding temperatures stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To the pH ≈ 5 that filtrates, remove spent acid with 5～15 ℃ of cold water washing filter cakes of temperature.Collect filter cake.Filtrating is deposited in the spent acid storage tank.
B, Sulphanilic Acid dissolving
In enamel pot, put into 1350 liters in end water, add Sulphanilic Acid 184.68Kg, transfer pH=7, material is dissolved entirely, clarification with 30% sodium hydroxide solution.Volume is 1800 liters, and the mass percent concentration of solution is 10%.
C, primary condensation
A step gained filter cake is joined in the Sulphanilic Acid solution adjustment temperature to 20 ℃.Keep pH=7～8 with 30% sodium hydroxide solution, stirring reaction 15～20 hours.20～25 ℃ of temperature of reaction, reaction pH=7～8.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
D, m-sulfanilic acid dissolving
In enamel pot, put into 700 liters in end water, add m-sulfanilic acid 174.2Kg, transfer pH=9, material is dissolved entirely, clarification with 30% sodium hydroxide solution.Volume is 1000 liters, and the mass percent concentration of solution is 17.5%.
E, secondary condensation
Put into 1000 liters of frozen water in the phase reaction jar, add cyanuric chloride 193.4Kg, material is mixed.0～5 ℃ of controlled temperature, control pH=2.5～3.5 added b step solution in 45～60 minutes, kept pH=2.5～3.5 with 10% yellow soda ash then, stirring reaction 3 hours.0～5 ℃ of temperature of reaction, reaction pH=2.5～3.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
F, three condensations
Quadrol 61Kg is added in the c solution, and insulated and stirred reaction 1 hour is warming up to 40 ℃, keeps pH=10～11 with 30% sodium hydroxide solution, stirring reaction 5 hours.40～45 ℃ of temperature of reaction, reaction pH=10～11.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
G, four condensations
C step gained condensated liquid is joined in three condensated liquids adjustment temperature to 35 ℃.Keep pH=10～11 with 30% sodium hydroxide solution, stirring reaction 18～20 hours.35～40 ℃ of temperature of reaction, reaction pH=10～11.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
H, interpolation auxiliary agent
With 50 kilograms sodium sulfate, mixed phosphate, one or more among Sodium hexametaphosphate 99, EDTA, the NNO join in the g step gained reaction solution, stir 15 minutes, and are subsequent use.
I, removal insolubles
H step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.3 the waste residue about kilogram is used for engineering soil.
J, purification
With the filtrating of collecting through membrane filtration, and with the concentration of the feed liquid percentage concentration 25% that improves the quality.One time membrane filtration waste water joins in the look liquid, continues membrane filtration.Secondary membrane filtration waste water as dyestuff at the bottom of water jacket use.
The adjustment of k, coloured light and intensity
From the reaction storage tank, extract feed liquid 200ml, dry and dyeing with small-sized spray drier.According to coloration result, add an amount of other batch dyestuff, carry out the coloured light adjustment.Add glucose in proportion according to the UV intensity of dyestuff again and Sodium sulfate anhydrous.min(99) carries out the adjustment of intensity.
L, drying
To join in the feed liquid preheater with regard to the look liquid of k step, adjust 210 ℃ of spray tower inlet temperatures, with 95～100 ℃ 5 carry out spraying drying.
M, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Get formula turquoise blue dyestuff
Can the Sulphanilic Acid among the step b be replaced with ORTHO AMINO PHENOL SULPHONIC or m-sulfanilic acid in addition.
Embodiment 4
A, chlorosulfonation, ice are analysed
In enamel pot, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc being added in 2 hours consuming time. 120 ℃ of adjustment temperature, 120～125 ℃ of holding temperatures were reacted 4 hours.65 ℃ of adjustment temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 490 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.90 ℃ of adjustment temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.105 ℃ of adjustment temperature.105～110 ℃ of holding temperatures were reacted 2 hours.
10～15 ℃ of temperature of adjustment join ice with the chlorosulphonation feed liquid of gained with thread and analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.5～15 ℃ of holding temperatures stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To the pH ≈ 5 that filtrates, remove spent acid with 5～15 ℃ of cold water washing filter cakes of temperature.Collect filter cake.Filtrating is deposited in the spent acid storage tank.
B, Sulphanilic Acid dissolving
In enamel pot, put into 1725 liters in end water, add Sulphanilic Acid 235.98Kg, transfer pH=7, material is dissolved entirely, clarification with 30% sodium hydroxide solution.Volume is 2300 liters, and the mass percent concentration of solution is 10%.
C, primary condensation
A step gained filter cake is joined in the Sulphanilic Acid solution adjustment temperature to 20 ℃.Keep pH=7～8 with 30% sodium hydroxide solution, stirring reaction 15～20 hours.20～25 ℃ of temperature of reaction, reaction pH=7～8.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
D, ORTHO AMINO PHENOL SULPHONIC dissolving
In enamel pot, put into 700 liters in end water, add ORTHO AMINO PHENOL SULPHONIC 174.2Kg, transfer pH=9, material is dissolved entirely, clarification with 30% sodium hydroxide solution.Volume is 1000 liters, and the mass percent concentration of solution is 17.5%.
E, secondary condensation
Put into 1000 liters of frozen water in the phase reaction jar, add cyanuric chloride 193.4Kg, material is mixed.0～5 ℃ of controlled temperature, control pH=2.5～3.5 added b step solution in 45～60 minutes, kept pH=2.5～3.5 with 10% yellow soda ash then, stirring reaction 3 hours.0～5 ℃ of temperature of reaction, reaction pH=2.5～3.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
F, three condensations
Quadrol 61Kg is added in the c solution, and insulated and stirred reaction 1 hour is warming up to 40 ℃, keeps pH=10～11 with 30% sodium hydroxide solution, stirring reaction 5 hours.40～45 ℃ of temperature of reaction, reaction pH=10～11.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
G, four condensations
C step gained condensated liquid is joined in three condensated liquids adjustment temperature to 35 ℃.Keep pH=10～11 with 30% sodium hydroxide solution, stirring reaction 18～20 hours.35～40 ℃ of temperature of reaction, reaction pH=10～11.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
H, interpolation auxiliary agent
With 50 kilograms sodium sulfate, mixed phosphate, one or more among Sodium hexametaphosphate 99, EDTA, the NNO join in the g step gained reaction solution, stir 15 minutes, and are subsequent use.
I, removal insolubles
H step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.3 the waste residue about kilogram is used for engineering soil.
G, purification
With the filtrating of collecting through membrane filtration, and with the concentration of the feed liquid percentage concentration 25% that improves the quality.One time membrane filtration waste water joins in the look liquid, continues membrane filtration.Secondary membrane filtration waste water as dyestuff at the bottom of water jacket use.
The adjustment of k, coloured light and intensity
From the reaction storage tank, extract feed liquid 200ml, dry and dyeing with small-sized spray drier.According to coloration result, add an amount of other batch dyestuff, carry out the coloured light adjustment.Add glucose in proportion according to the UV intensity of dyestuff again and Sodium sulfate anhydrous.min(99) carries out the adjustment of intensity.
L, drying
To join in the feed liquid preheater with regard to the look liquid of k step, adjust 210 ℃ of spray tower inlet temperatures, with 95～100 ℃ 5 carry out spraying drying.
M, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Get formula turquoise blue dyestuff
Can the Sulphanilic Acid among the step b be replaced with ORTHO AMINO PHENOL SULPHONIC or m-sulfanilic acid in addition.
Embodiment 5
A, chlorosulfonation, ice are analysed
In enamel pot, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc being added in 2 hours consuming time. 120 ℃ of adjustment temperature, 120～125 ℃ of holding temperatures were reacted 4 hours.65 ℃ of adjustment temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 490 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.90 ℃ of adjustment temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.105 ℃ of adjustment temperature.105～110 ℃ of holding temperatures were reacted 2 hours.
10～15 ℃ of temperature of adjustment join ice with the chlorosulphonation feed liquid of gained with thread and analyse in the jar controlled temperature.2 hours consuming time, the chlorosulphonation feed liquid is added.5～15 ℃ of holding temperatures stirred 1 hour.Ice is analysed liquid join in the solid-liquid separator, separate.To the pH ≈ 5 that filtrates, remove spent acid with 5～15 ℃ of cold water washing filter cakes of temperature.Collect filter cake.Filtrating is deposited in the spent acid storage tank.
B, Sulphanilic Acid dissolving
In enamel pot, put into 1125 liters in end water, add Sulphanilic Acid 153.9Kg, transfer pH=7, material is dissolved entirely, clarification with 30% sodium hydroxide solution.Volume is 1500 liters, and the mass percent concentration of solution is 10%.
C, primary condensation
A step gained filter cake is joined in the Sulphanilic Acid solution adjustment temperature to 20 ℃.Keep pH=7～8 with 30% sodium hydroxide solution, stirring reaction 15～20 hours.20～25 ℃ of temperature of reaction, reaction pH=7～8.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
D, Sulphanilic Acid dissolving
In enamel pot, put into 700 liters in end water, add Sulphanilic Acid 174.2Kg, transfer pH=9, material is dissolved entirely, clarification with 30% sodium hydroxide solution.Volume is 1000 liters, and the mass percent concentration of solution is 17.5%.
E, secondary condensation
Put into 1000 liters of frozen water in the phase reaction jar, add cyanuric chloride 193.4Kg, material is mixed.0～5 ℃ of controlled temperature, control pH=2.5～3.5 added b step solution in 45～60 minutes, kept pH=2.5～3.5 with 10% yellow soda ash then, stirring reaction 3 hours.0～5 ℃ of temperature of reaction, reaction pH=2.5～3.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
F, three condensations
Quadrol 61Kg is added in the c solution, and insulated and stirred reaction 1 hour is warming up to 40 ℃, keeps pH=10～11 with 30% sodium hydroxide solution, stirring reaction 5 hours.40～45 ℃ of temperature of reaction, reaction pH=10～11.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
G, four condensations
C step gained condensated liquid is joined in three condensated liquids adjustment temperature to 35 ℃.Keep pH=10～11 with 30% sodium hydroxide solution, stirring reaction 18～20 hours.35～40 ℃ of temperature of reaction, reaction pH=10～11.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
H, interpolation auxiliary agent
With 50 kilograms sodium sulfate, mixed phosphate, one or more among Sodium hexametaphosphate 99, EDTA, the NNO join in the g step gained reaction solution, stir 15 minutes, and are subsequent use.
I, removal insolubles
H step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.3 the waste residue about kilogram is used for engineering soil.
J, purification
With the filtrating of collecting through membrane filtration, and with the concentration of the feed liquid percentage concentration 25% that improves the quality.One time membrane filtration waste water joins in the look liquid, continues membrane filtration.Secondary membrane filtration waste water as dyestuff at the bottom of water jacket use.
The adjustment of k, coloured light and intensity
From the reaction storage tank, extract feed liquid 200ml, dry and dyeing with small-sized spray drier.According to coloration result, add an amount of other batch dyestuff, carry out the coloured light adjustment.Add glucose in proportion according to the UV intensity of dyestuff again and Sodium sulfate anhydrous.min(99) carries out the adjustment of intensity.
L, drying
To join in the feed liquid preheater with regard to the look liquid of k step, adjust 210 ℃ of spray tower inlet temperatures, with 95～100 ℃ 5 carry out spraying drying.
M, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.Get formula turquoise blue dyestuff
Can the Sulphanilic Acid among the step b be replaced with ORTHO AMINO PHENOL SULPHONIC or m-sulfanilic acid in addition.
Embodiment 6
A, chlorosulfonation, ice are analysed
In enamel pot, add 1750 kilograms of chlorsulfonic acids. circulating water cooling, 40～50 ℃ of controlled temperature.CuPc being added in 2 hours consuming time. 123 ℃ of adjustment temperature, 123～128 ℃ of holding temperatures were reacted 4 hours.65 ℃ of adjustment temperature, 65～70 ℃ of holding temperatures, 2 hours consuming time with 560 kilograms of addings of sulfur oxychloride.65～70 ℃ of holding temperatures were reacted 2 hours.90 ℃ of adjustment temperature, 90～95 ℃ of holding temperatures were reacted 1 hour.103 ℃ of adjustment temperature.103～108 ℃ of holding temperatures were reacted 2 hours.
20～25 ℃ of temperature of adjustment join ice with the chlorosulphonation feed liquid of gained with thread and 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 the pH ≈ 3 that filtrates, remove spent acid with temperature-5～5 ℃ cold water washing filter cake.Collect filter cake.Filtrating is deposited in the spent acid storage tank.
B, Sulphanilic Acid dissolving
In enamel pot, put into 1125 liters in end water, add Sulphanilic Acid 153.9Kg, transfer pH=7, material is dissolved entirely, clarification with 30% sodium hydroxide solution.Volume is 1500 liters, and the mass percent concentration of solution is 10%.
C, primary condensation
A step gained filter cake is joined in the Sulphanilic Acid solution adjustment temperature to 20 ℃.Keep pH=7～8 with 30% sodium hydroxide solution, stirring reaction 15～20 hours.20～25 ℃ of temperature of reaction, reaction pH=7～8.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
D, the β hydroxyethyl sulfone sulfate ester aniline is dissolved
In enamel pot, put into 3000 liters in end water, add, transfer pH=4, material is dissolved entirely, clarification with 15% sodium carbonate solution to β hydroxyethyl sulfone sulfate ester aniline 333Kg.Volume is 4150 liters, and the mass percent concentration of solution is 8%.
E, secondary condensation
Put into 1000 liters of frozen water in the phase reaction jar, add cyanuric chloride 227.5Kg, material is mixed.0～5 ℃ of controlled temperature, control pH=2～3 added b step solution in 45～60 minutes, kept pH=2～3 with 10% yellow soda ash then, stirring reaction 3 hours.0～5 ℃ of temperature of reaction, reaction pH=2～3.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
F, three condensations
Ammoniacal liquor 81Kg with 25% adds in the c solution, and insulated and stirred reaction 1 hour is warming up to 40 ℃, keeps pH=7～8 with 10% sodium carbonate solution, stirring reaction 5 hours.40～45 ℃ of temperature of reaction, reaction pH=7～8.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
G, four condensations
C step gained condensated liquid is joined in three condensated liquids adjustment temperature to 35 ℃.Keep pH=8～9 with 30% sodium hydroxide solution, stirring reaction 15～20 hours.35～40 ℃ of temperature of reaction, reaction pH=8～9.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
H, interpolation auxiliary agent
With 50 kilograms sodium sulfate, mixed phosphate, one or more among Sodium hexametaphosphate 99, EDTA, the NNO join in the g step gained reaction solution, stir 15 minutes, and are subsequent use.
I, removal insolubles
H step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.3 the waste residue about kilogram is used for engineering soil.
J, purification
With the filtrating of collecting through membrane filtration, and with the concentration of the feed liquid percentage concentration 25% that improves the quality.One time membrane filtration waste water joins in the look liquid, continues membrane filtration.Secondary membrane filtration waste water as dyestuff at the bottom of water jacket use.
The adjustment of k, coloured light and intensity
From the reaction storage tank, extract feed liquid 200ml, dry and dyeing with small-sized spray drier.According to coloration result, add an amount of other batch dyestuff, carry out the coloured light adjustment.Add glucose in proportion according to the UV intensity of dyestuff again and Sodium sulfate anhydrous.min(99) carries out the adjustment of intensity.
L, drying
The look liquid of k step is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying with 95～100 ℃ temperature outs.
M, the packing of product
The dyestuff of spraying drying gained is packed by the specification of 25 kilograms in every case.. get the emerald green blue dye of formula
With in the d step β hydroxyethyl sulfone sulfate ester aniline being replaced adjacent β hydroxyethyl sulfone sulfate ester aniline, get the emerald green blue dye of formula in addition:
When in the d step β hydroxyethyl sulfone sulfate ester aniline being replaced with a β hydroxyethyl sulfone sulfate ester aniline, the emerald green blue dye of formula:
In the time of can the Sulphanilic Acid among the step b being replaced ORTHO AMINO PHENOL SULPHONIC in addition, get the emerald green blue dye of formula:
When the Sulphanilic Acid among the step b replaces with m-sulfanilic acid, get the emerald green blue dye of formula:
Claims (6)
1. turquoise blue chemically-reactive dyes is characterized in that this dyestuff has following general structure:
X+y=3.5 wherein, x＞0, y＞0;
R
1For:
2. dyestuff according to claim 1, R
1For
3. the preparation method of dyestuff according to claim 1, this method comprises the steps:
A, chlorosulfonation, ice are analysed
The cooling of adding chlorsulfonic acid circulating water after the reaction of adding CuPc, adds the sulfur oxychloride reaction again in enamel pot, gets the chlorosulphonation feed liquid; Adjust temperature once more, the chlorosulphonation feed liquid of gained is joined ice with thread analyse in the jar, controlled temperature stirs; Obtain ice and analyse liquid, ice is analysed liquid join in the solid-liquid separator, separate; The cold water washing filter cake is removed spent acid to the pH=7 that filtrates, and collects filter cake;
B, A substance dissolves
The A substance dissolves in water, is transferred pH=7 with 30% sodium hydroxide solution, material is dissolved entirely; Wherein the A material is a kind of in Sulphanilic Acid, m-sulfanilic acid, the ORTHO AMINO PHENOL SULPHONIC;
C, primary condensation
A step gained filter cake is joined in the b step gained solution, keep pH=7～8 with 30% sodium hydroxide solution, stirring reaction, reaction pH=7～8 are used the aluminium base silica gel thin-layer plate endpoint detection of TLC at last;
D, secondary condensation
With adding cyanuric chloride solution in the solution of B material, keep pH=2～4 with 10% yellow soda ash, stirring reaction, pH=2～4 are used the aluminium base silica gel thin-layer plate endpoint detection of TLC at last; Wherein the B material is an aniline-2,5-disulfonic acid, m-sulfanilic acid, Sulphanilic Acid, ORTHO AMINO PHENOL SULPHONIC, a kind of in β hydroxyethyl sulfone sulfate ester aniline, a β hydroxyethyl sulfone sulfate ester aniline, the adjacent β hydroxyethyl sulfone sulfate ester aniline;
E, three condensations
The solution of C material is added in the d step gained solution, behind the stirring reaction, with the aluminium base silica gel thin-layer plate endpoint detection of TLC, must three condensated liquids, the C material is 2, a kind of in 4-diamino benzene sulfonic acid sodium, ammoniacal liquor, the quadrol;
F, four condensations
C step gained solution is joined in three condensated liquids, keep pH=7～9 with 30% sodium hydroxide solution, stirring reaction is used the aluminium base silica gel thin-layer plate endpoint detection of TLC at last; Obtain the product of structural formula (I).
4. preparation method according to claim 3, this method also comprises the post-processing step of product, and this post-processing step comprises:
G, interpolation auxiliary agent
With sodium sulfate, mixed phosphate, one or more among Sodium hexametaphosphate 99, EDTA, the NNO join in the product solution of structural formula (I), stir, and are subsequent use;
H, removal insolubles
G step gained reaction solution is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank;
I, purification
With the feed liquid of collecting through membrane filtration, and with the concentration of the feed liquid percentage concentration 25% that improves the quality.One time membrane filtration waste water joins in the look liquid, continues membrane filtration.Secondary membrane filtration waste water as dyestuff at the bottom of water jacket use;
The adjustment of j, coloured light and intensity
From the reaction storage tank, extract feed liquid 200ml, dry and dyeing with small-sized spray drier; According to coloration result, add an amount of other batch dyestuff, carry out the coloured light adjustment, add glucose in proportion according to the UV intensity of dyestuff again and Sodium sulfate anhydrous.min(99) carries out the adjustment of intensity;
K, drying
The look liquid of j step is joined in the feed liquid preheater, adjust 210 ℃ of spray tower inlet temperatures, carry out spraying drying with 95～100 ℃ temperature outs.
5. the described dyestuff of claim 1 is in the dyeing of hydroxyl or nitrogenous fibre materials or the application in the stamp.
6. the application of dyestuff according to claim 1 in fabric fiber material, paper or plastics film being printed dyeing or stamp through ink jet printing method.
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| CN108017927A (en) * | 2017-12-04 | 2018-05-11 | 南通龙翔新材料科技股份有限公司 | A kind of organic pigment sulfonyl chloride derivatives preparation method |
| CN115491909A (en) * | 2022-09-05 | 2022-12-20 | 愉悦家纺有限公司 | Color stereo based on gridding blending of nine-primary-color dye solution and construction of equal brightness chromatogram thereof |
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| CN108017927A (en) * | 2017-12-04 | 2018-05-11 | 南通龙翔新材料科技股份有限公司 | A kind of organic pigment sulfonyl chloride derivatives preparation method |
| CN115491909A (en) * | 2022-09-05 | 2022-12-20 | 愉悦家纺有限公司 | Color stereo based on gridding blending of nine-primary-color dye solution and construction of equal brightness chromatogram thereof |
| CN115491909B (en) * | 2022-09-05 | 2024-02-02 | 愉悦家纺有限公司 | Color space based on gridding mixing of nine-primary color dye liquor and equal brightness color spectrum construction thereof |
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