CN101481523A - Red reactive dye for fur and preparation thereof - Google Patents
Red reactive dye for fur and preparation thereof Download PDFInfo
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- CN101481523A CN101481523A CNA2008101541080A CN200810154108A CN101481523A CN 101481523 A CN101481523 A CN 101481523A CN A2008101541080 A CNA2008101541080 A CN A2008101541080A CN 200810154108 A CN200810154108 A CN 200810154108A CN 101481523 A CN101481523 A CN 101481523A
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Abstract
The invention discloses a red reactive dye used for fur and a preparation method thereof. The red reactive dye used for fur takes 2, 4-diaminobenzene sodium sulfonate, 1-naphthol-5-sulfoacid, 2, 3-dichloro propionyl chloride as main raw materials. The red reactive dye of the invention is prepared by condensation, diazotization, coincidence, chromatic light adjustment, intensity adjustment, drying and packaging. The red reactive dye used for fur in the invention has relatively high responsiveness, good solubility and bright-colored and beautiful chromatic light; in addition, the light fastness property is relatively good, the exhaustion rate and the color fixing rate are very high. The pre-blending technology and the virgin stock spraying technology are adopted after film processing. Therefore, waste water and waste residue are not generated, greatly contributing to the environmental protection.
Description
Technical field
The present invention relates to a kind of reactive dye for wool and preparation method thereof, especially red reactive dye for wool 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 large red reactive dyestuffs and preparation method thereof.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of red reactive dye for wool has following general structure
Wherein
In a kind of.
R represents low alkyl group in the formula, is preferably the alkyl of 1-3 carbon atom, more preferably methyl and/or ethyl.
Preferably, described dyestuff is:
In addition, the present invention also provides a kind of preparation method of red reactive dye for wool, comprises the steps:
A. with 2.4-diamino benzene sulfonic acid sodium, the Ursol D ortho-sulfonic acid, para-ester or sulfonation para-ester are through condensation reaction and diazotization reaction, and perhaps direct diazotization reaction prepares diazotization reaction liquid;
Wherein said condensation reaction and diazotization reaction are the known popular responses of those of ordinary skills, and those of ordinary skills need not creative work and can implement.
B. add 1-naphthol-5-sulfonic acid in water, make material dissolution under stirring, clarification makes C%=4-6 in the solution, preferred 4.9-5.
C. coupled reaction: with thionamic acid nitrous acid excessive among the step a is eliminated, then this solution is followed acid binding agent to join in the solution of step b, control pH value of solution=6-8, preferred 7, holding temperature 5-25 ℃, react preferably 2.5-3 hour 2-4 hour;
D. remove insolubles: c step reaction liquid is transferred to pH=6-6.5, preferably regulate with 30% hydrochloric acid soln; Stirred 10-20 minute, reaction solution is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects filtrate, behind membrane filtration, makes feed concentration to C%=20-30 filtrate, and preferred 25; Promptly obtain red reactive dye for wool of the present invention.
Preferably also comprise the steps:
E. piece together before and mix: d step look liquid with small-sized spray tower drying, dyeing, is carried out the adjustment of coloured light and intensity again according to coloration result;
More preferably also comprise the steps:
F. dry: as the look liquid of step e to be joined in the feed liquid preheating container, adjust 210 ℃ of inlet temperatures, carry out spraying drying, obtain red reactive dye for wool with 95～100 ℃ temperature outs.
Described step a is: in water, adds 2.4-diamino benzene sulfonic acid sodium, stirs 20-25 ℃ of controlled temperature, and material dissolution, clarification adds dilute hydrochloric acid regulator solution pH=6-6.5, C%=10-11 in the solution; On the rocksly in solution be cooled to 0-5 ℃, in 1-1.5 hour, add 2,3-two chlorpromazine chlorides, stirring reaction, temperature of reaction 0-5 ℃, reaction pH=6-6.5; 30% hydrochloric acid soln that adds, adjust volume, C%=7, adjust temperature to 5-7 ℃, guarantee to be after congo-red test paper soaks blue at reaction soln, and the KI test paper being little blueness after soaking, is 30% sodium nitrite solution adding with mass percent concentration with 30-60 minute time, holding temperature 8-10 ℃, reacted 2 hours.
Described step b is: add 1-naphthol-5-sulfonic acid in water, make material dissolution under stirring, clarification, C%=4.9-5 in the solution.
Described step c is: with thionamic acid nitrous acid excessive among the step a eliminated, then this solution followed acid binding agent to join among the step b, and control pH value of solution=7, holding temperature 5-25 ℃, keep PH=7-7.5, reacted 2.5-3 hour;
Preferably:
The employed alkali of described step a is sodium bicarbonate.
The employed acid binding agent of described step c is 15% soda ash solution.
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: red reactive dye used for fur of the present invention has higher reactivity, 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.Preceding assembly after film is handled mixes the method for technology and magma spraying.Can stop the generation of waste water and waste residue, environment protection has been played very big promoter action.
Description of drawings
Fig. 1 is preparation technology's schema of red reactive dye for wool of the present invention.
Embodiment 1
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
2,4-diamino benzene sulfonic acid sodium 210 1 288.75 1.375
2,3-two chlorpromazine chlorides 161.5 1.05 233.2 1.375
Sodium Nitrite 69 1.02 96.77 1.375
Hydrochloric acid 36.5 2.5 125.47 1.375
1-naphthol-5-sulfonic acid 246 0.98 331.49 1.375
2, dyestuff preparation technology of the present invention operates as follows:
A, 2, the dissolving of 4-diamino benzene sulfonic acid sodium
Put into 2400 liters in end water in retort, add 2,288.75 kilograms in 4-diamino benzene sulfonic acid sodium is warming up to 22 ℃, and stirring and dissolving makes material molten entirely, clarification.Transfer pH=6～6.5 with dilute hydrochloric acid.Volume is 2625 liters, C%=11 in the solution (referring to mass percent concentration, down together).
B, condensation reaction
The temperature of adjusting a solution with direct ice and chuck circulating water is 0～5 ℃, adjusts C%=10 in the solution, and with 2,3-two chlorpromazine chlorides add, and keep pH=6～6.5 with sodium bicarbonate simultaneously, stirring reaction 2 hours in 1～1.5 hour.0～5 ℃ of temperature of reaction, reaction pH=6～6.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
C, diazotization reaction
Quantitative 30% hydrochloric acid soln is joined in the condensated liquid.Adjust 5～7 ℃ of solution temperatures with direct ice, adjust volume to 8330 liter, guarantee to be after congo-red test paper soaks blue at reaction soln; And starch potassium iodide paper is the time of 30～60 minutes following times spent of condition of little blueness after soaking quantitative 30% sodium nitrite solution is added.8～10 ℃ of holding temperatures were reacted 2 hours.
The dissolving of d, 1-naphthol-5-sulfonic acid: (L acid)
In L acidifying batch can, add 2500 liters in water, add 331.49 kilograms of 100%L acid.Stirred 15 minutes, and made material dissolution, clarification.The water adjustment is mentioned to 6000 liters.C%=5.5 in the solution.
E, coupled reaction
With thionamic acid nitrous acid excessive in the diazotization reaction liquid is eliminated.Then this solution is joined in the 1-naphthol-5-sulfonic acid solution.Transfer pH=7 with 15% soda ash solution.Holding temperature 10-15 ℃, keep pH=7-7.5, reacted 3 hours.
F, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln.Stirred 15 minutes.
G, removal insolubles
G step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.5 the waste residue about kilogram is used for engineering soil.
H, purification
The filtrate of collecting through membrane filtration, and is increased to C%=25 with the concentration of feed liquid.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 i, coloured light and intensity
From the reaction storage tank, extract feed liquid 200ml, with dry drying of small-sized spraying and dyeing.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.
J, 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.
K, 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.1200 kilograms of this 1.375 moles of gained, 100% dyestuffs.
Preparation red reactive dye for wool norm quota of consumption table of the present invention:
| Material name | Unit consumption, Kg/T |
| 2,4-diamino benzene sulfonic acid sodium | 241 |
| 2,3-two chlorpromazine chlorides | 195 |
| 1-naphthol-5-sulfonic acid | 276 |
| Hydrochloric acid | 400 |
| Sodium Nitrite | 81 |
| Soda ash | 172 |
| Sodium bicarbonate | 286 |
Preparation red reactive dye for wool application performance table of the present invention
Embodiment 2
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
2,4-diamino benzene sulfonic acid sodium 210 1 288.75 1.375
2,3-two chlorpromazine chlorides 161.5 1.05 233.2 1.375
Sodium Nitrite 69 1.02 96.77 1.375
Hydrochloric acid 36.5 2.5 125.47 1.375
1-naphthol-5-sulfonic acid 246 0.98 331.49 1.375
2, dyestuff preparation technology of the present invention operates as follows:
A, 2, the dissolving of 4-diamino benzene sulfonic acid sodium
Put into 2400 liters in end water in retort, add 2,288.75 kilograms in 4-diamino benzene sulfonic acid sodium is warming up to 22 ℃, and stirring and dissolving makes material molten entirely, clarification.Transfer pH=6～6.5 with dilute hydrochloric acid.Volume is 2625 liters, C%=11 in the solution (referring to mass percent concentration, down together).
B, condensation reaction
The temperature of adjusting a solution with direct ice and chuck circulating water is 0～5 ℃, adjusts C%=10 in the solution, and with 2,3-two chlorpromazine chlorides add, and keep pH=6～6.5 with sodium bicarbonate simultaneously, stirring reaction 2 hours in 1～1.5 hour.0～5 ℃ of temperature of reaction, reaction pH=6～6.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
C, diazotization reaction
Quantitative 30% hydrochloric acid soln is joined in the condensated liquid.Adjust 5～7 ℃ of solution temperatures with direct ice, adjust volume to 8330 liter, guarantee to be after congo-red test paper soaks blue at reaction soln; And starch potassium iodide paper is the time of 30～60 minutes following times spent of condition of little blueness after soaking quantitative 30% sodium nitrite solution is added.8～10 ℃ of holding temperatures were reacted 2 hours.
The dissolving of d, 1-naphthol-5-sulfonic acid: (L acid)
In L acidifying batch can, add 2500 liters in water, add 331.49 kilograms of 100%L acid.Stirred 15 minutes, and made material dissolution, clarification.The water adjustment is mentioned to 6000 liters.C%=5.5 in the solution.
E, coupled reaction
With thionamic acid nitrous acid excessive in the diazotization reaction liquid is eliminated.Then this solution is joined in the 1-naphthol-5-sulfonic acid solution.Transfer pH=7 with 15% soda ash solution.Holding temperature 15-20 ℃, keep pH=7-7.5, reacted 3 hours.
F, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln.Stirred 15 minutes.
G, removal insolubles
G step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.5 the waste residue about kilogram is used for engineering soil.
H, purification
The filtrate of collecting through membrane filtration, and is increased to C%=25 with the concentration of feed liquid.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 i, coloured light and intensity
From the reaction storage tank, extract feed liquid 200ml, with dry drying of small-sized spraying and dyeing.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.
J, 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.
K, 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.1210 kilograms of this 1.375 moles of gained, 100% dyestuffs.
Embodiment 3
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
2,4-diamino benzene sulfonic acid sodium 210 1 288.75 1.375
2,3-two chlorpromazine chlorides 161.5 1.05 233.2 1.375
Sodium Nitrite 69 1.02 96.77 1.375
Hydrochloric acid 36.5 2.5 125.47 1.375
1-naphthol-5-sulfonic acid 246 0.98 331.49 1.375
2, dyestuff preparation technology of the present invention operates as follows:
A, 2, the dissolving of 4-diamino benzene sulfonic acid sodium
Put into 2400 liters in end water in retort, add 2,288.75 kilograms in 4-diamino benzene sulfonic acid sodium is warming up to 22 ℃, and stirring and dissolving makes material molten entirely, clarification.Transfer pH=6～6.5 with dilute hydrochloric acid.Volume is 2625 liters, C%=11 in the solution (referring to mass percent concentration, down together).
B, condensation reaction
The temperature of adjusting a solution with direct ice and chuck circulating water is 0～5 ℃, adjusts C%=10 in the solution, and with 2,3-two chlorpromazine chlorides add, and keep pH=6～6.5 with sodium bicarbonate simultaneously, stirring reaction 2 hours in 1～1.5 hour.0～5 ℃ of temperature of reaction, reaction pH=6～6.5.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
C, diazotization reaction
Quantitative 30% hydrochloric acid soln is joined in the condensated liquid.Adjust 5～7 ℃ of solution temperatures with direct ice, adjust volume to 8330 liter, guarantee to be after congo-red test paper soaks blue at reaction soln; And starch potassium iodide paper is the time of 30～60 minutes following times spent of condition of little blueness after soaking quantitative 30% sodium nitrite solution is added.8～10 ℃ of holding temperatures were reacted 2 hours.
The dissolving of d, 1-naphthol-5-sulfonic acid: (L acid)
In L acidifying batch can, add 2500 liters in water, add 331.49 kilograms of 100%L acid.Stirred 15 minutes, and made material dissolution, clarification.The water adjustment is mentioned to 6000 liters.C%=5.5 in the solution.
E, coupled reaction
With thionamic acid nitrous acid excessive in the diazotization reaction liquid is eliminated.Then this solution is joined in the 1-naphthol-5-sulfonic acid solution.Transfer pH=7 with 15% soda ash solution.Holding temperature 20-25 ℃, keep pH=7-7.5, reacted 3 hours.
F, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln.Stirred 15 minutes.
G, removal insolubles
G step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.5 the waste residue about kilogram is used for engineering soil.
H, purification
The filtrate of collecting through membrane filtration, and is increased to C%=25 with the concentration of feed liquid.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.
, coloured light and intensity adjustment
From the reaction storage tank, extract feed liquid 200ml, with dry drying of small-sized spraying and dyeing.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.
J, 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.
K, 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.1225 kilograms of this 1.375 moles of gained, 100% dyestuffs.
Embodiment 4
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
Ursol D ortho-sulfonic acid 188 1 258.5 1.375
2,3-two chlorpromazine chlorides 161.5 1.05 233.2 1.375
Sodium Nitrite 69 1.02 96.77 1.375
Hydrochloric acid 36.5 2.5 125.47 1.375
1-naphthol-5-sulfonic acid 246 0.98 331.49 1.375
2, dyestuff preparation technology of the present invention operates as follows:
The dissolving of a, Ursol D ortho-sulfonic acid
In retort, put into 2400 liters in end water, add 258.5 kilograms of Ursol D ortho-sulfonic acids, be warming up to 35 ℃, transfer the pH=7.5-8 stirring and dissolving, make material molten entirely, clarification with yellow soda ash.Volume is 2350 liters, C%=11 in the solution (referring to mass percent concentration, down together).
B, condensation reaction
The temperature of adjusting a solution with direct ice and chuck circulating water is 0～5 ℃, adjusts C%=10 in the solution, and with 2,3-two chlorpromazine chlorides add, and keep pH=7.5-8 with 15% sodium carbonate solution simultaneously, stirring reaction 2 hours in 1～1.5 hour.0～5 ℃ of temperature of reaction, reaction pH=7.5-8.Use the aluminium base silica gel thin-layer plate endpoint detection of TLC at last.
C, diazotization reaction
Quantitative 30% hydrochloric acid soln is joined in the condensated liquid.Adjust 5～7 ℃ of solution temperatures with direct ice, adjust volume to 8330 liter, guarantee to be after congo-red test paper soaks blue at reaction soln; And starch potassium iodide paper is the time of 30～60 minutes following times spent of condition of little blueness after soaking quantitative 30% sodium nitrite solution is added.8～10 ℃ of holding temperatures were reacted 2 hours.
The dissolving of d, 1-naphthol-5-sulfonic acid: (L acid)
In L acidifying batch can, add 2500 liters in water, add 331.49 kilograms of 100%L acid.Stirred 15 minutes, and made material dissolution, clarification.The water adjustment is mentioned to 6000 liters.C%=5.5 in the solution.
E, coupled reaction
With thionamic acid nitrous acid excessive in the diazotization reaction liquid is eliminated.Then this solution is joined in the 1-naphthol-5-sulfonic acid solution.Transfer pH=7 with 15% soda ash solution.Holding temperature 20-25 ℃, keep pH=7-7.5, reacted 3 hours.
F, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln.Stirred 15 minutes.
G, removal insolubles
G step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.5 the waste residue about kilogram is used for engineering soil.
H, purification
The filtrate of collecting through membrane filtration, and is increased to C%=25 with the concentration of feed liquid.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.
, coloured light and intensity adjustment
From the reaction storage tank, extract feed liquid 200ml, with dry drying of small-sized spraying and dyeing.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.
J, 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.
K, 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.1210 kilograms of this 1.375 moles of gained, 100% dyestuffs.
Embodiment 5
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
Para-ester 281 1 386.38 1.375
Hydrochloric acid 36.5 1.3 65.24 1.375
Sodium Nitrite 69 1.02 96.77 1.375
1-naphthol-5-sulfonic acid 246 0.98 331.49 1.375
2, dyestuff preparation technology of the present invention operates as follows:
The dissolving of a, para-ester
In retort, put into 2400 liters in end water, add 386.4 kilograms of para-esters, stirred 15 minutes.
B, diazotization reaction
Quantitative 30% hydrochloric acid soln is joined in the para-ester solution.Adjust solution temperature with direct ice and be lower than 0 ℃, adjust volume to 8330 liter, guarantee to be after congo-red test paper soaks blue at reaction soln; And starch potassium iodide paper is the time of 1～2 minute following time spent of condition of little blueness after soaking quantitative 30% sodium nitrite solution is added.0～5 ℃ of holding temperature was reacted 2 hours.
The dissolving of d, 1-naphthol-5-sulfonic acid: (L acid)
In L acidifying batch can, add 2500 liters in water, add 331.49 kilograms of 100%L acid.Stirred 15 minutes, and made material dissolution, clarification.The water adjustment is mentioned to 6000 liters.C%=5.5 in the solution.
E, coupled reaction
With thionamic acid nitrous acid excessive in the diazotization reaction liquid is eliminated.Then this solution is joined in the 1-naphthol-5-sulfonic acid solution.Transfer pH=7 with 15% soda ash solution.Holding temperature 20-25 ℃, keep pH=7-7.5, reacted 3 hours.
F, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln.Stirred 15 minutes.
G, removal insolubles
G step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.5 the waste residue about kilogram is used for engineering soil.
H, purification
The filtrate of collecting through membrane filtration, and is increased to C%=25 with the concentration of feed liquid.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.
, coloured light and intensity adjustment
From the reaction storage tank, extract feed liquid 200ml, with dry drying of small-sized spraying and dyeing.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.
J, 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.
K, 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.1300 kilograms of this 1.375 moles of gained, 100% dyestuffs.
Embodiment 6
1, allocation sheet:
The material name weight molecule is than folding hundred consumptions (Kg) charging capacitys (kilomol)
Sulfonation para-ester 361 1 496.38 1.375
Hydrochloric acid 36.5 1.3 65.24 1.375
Sodium Nitrite 69 1.02 96.77 1.375
1-naphthol-5-sulfonic acid 246 0.98 331.49 1.375
2, dyestuff preparation technology of the present invention operates as follows:
The dissolving of a, sulfonation para-ester
In retort, put into 2400 liters in end water, add 496.4 kilograms of sulfonation para-ester, stirred 15 minutes.
B, diazotization reaction
Quantitative 30% hydrochloric acid soln is joined in the sulfonation para-ester solution.Adjust solution temperature with direct ice and be lower than 0 ℃, adjust volume to 8330 liter, guarantee to be after congo-red test paper soaks blue at reaction soln; And starch potassium iodide paper is the time of 2.5～3 hours following times spent of condition of little blueness after soaking quantitative 30% sodium nitrite solution is added.0～5 ℃ of holding temperature was reacted 3 hours.
The dissolving of d, 1-naphthol-5-sulfonic acid: (L acid)
In L acidifying batch can, add 2500 liters in water, add 331.49 kilograms of 100%L acid.Stirred 15 minutes, and made material dissolution, clarification.The water adjustment is mentioned to 6000 liters.C%=5.5 in the solution.
E, coupled reaction
With thionamic acid nitrous acid excessive in the diazotization reaction liquid is eliminated.Then this solution is joined in the 1-naphthol-5-sulfonic acid solution.Transfer pH=7 with 15% soda ash solution.Holding temperature 20-25 ℃, keep pH=7-7.5, reacted 3 hours.
F, neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln.Stirred 15 minutes.
G, removal insolubles
G step reaction liquid is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collects feed liquid simultaneously in storage tank.1.5 the waste residue about kilogram is used for engineering soil.
H, purification
The filtrate of collecting through membrane filtration, and is increased to C%=25 with the concentration of feed liquid.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.
, coloured light and intensity adjustment
From the reaction storage tank, extract feed liquid 200ml, with dry drying of small-sized spraying and dyeing.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.
J, 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.
K, 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.1450 kilograms of this 1.375 moles of gained, 100% dyestuffs.
Example 1,2,3 resulting dyestuffs after testing.Compare with the standard of being formulated in the test, all up to standard.Example 3 Dry Sacks are more.Example 4 coloured light are dark partially.Example 5, example 6 performances are qualified.
Because the present invention adopts spraying drying, adopt with prior art that to dry resulting dyestuff crystal formation different, so the solubleness of the red reactive dye for wool of preparation method of the present invention preparation is big, 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, those of ordinary skills should be understood that, under the prerequisite that does not break away from spirit of the present invention, those of ordinary skills can make various changes or change to the present invention, and these changes and adjust all fall within the scope of the present invention.Protection scope of the present invention is determined with appending claims and equivalent thereof.
Claims (10)
1. a red reactive dye for wool is characterized in that, has following general structure
Wherein
In a kind of,
In the formula, R is a low alkyl group.
2, red reactive dye for wool according to claim 1 is characterized in that, described R represents C
1-C
3Alkyl.
3, red reactive dye for wool according to claim 1 and 2 is characterized in that, described R represents methyl and/or ethyl.
4, red reactive dye for wool according to claim 3 is characterized in that, described dyestuff is
5, a kind of preparation method of each described red reactive dye for wool of claim 1-4 comprises the steps:
A. with 2.4-diamino benzene sulfonic acid sodium, the Ursol D ortho-sulfonic acid, para-ester or sulfonation para-ester are through condensation reaction and diazotization reaction, and perhaps direct diazotization reaction prepares diazotization reaction liquid;
B. add 1-naphthol-5-sulfonic acid in water, make material dissolution under stirring, clarification makes C%=4-6 in the solution;
C. coupled reaction: with thionamic acid nitrous acid excessive among the step a is eliminated, then this solution is followed acid binding agent to join in the solution of step b, control pH value of solution=6-8, reacted 2-4 hour by holding temperature 5-25 ℃;
D. remove insolubles: c step reaction liquid is transferred to pH=6-6.5, stirred 10-20 minute, reaction solution is joined in the solid-liquid separator, separate, washery refuse is removed insolubles, collect filtrate, behind membrane filtration, make feed concentration filtrate, promptly obtain red reactive dye for wool of the present invention to C%=20-30.
6, method according to claim 5 also comprises the steps:
E. piece together before and mix: d step look liquid with small-sized spray tower drying, dyeing, is carried out the adjustment of coloured light and intensity again according to coloration result.
7, method according to claim 6 also comprises the steps:
F. dry: as the look liquid of step e to be joined in the feed liquid preheating container, adjust 210 ℃ of inlet temperatures, carry out spraying drying, obtain red reactive dye for wool with 95～100 ℃ temperature outs.
8, according to each described method of claim 5-8, it is characterized in that the C%=4.9-5 among the step b; PH among the step c is controlled at 7, reacts 2.5-3 hour; Regulate the pH value with 30% hydrochloric acid soln in the steps d, after the filtration, the concentration that makes feed liquid is to C%=25.
9, the preparation method of red reactive dye for wool according to claim 5, it is characterized in that, described step a is: add 2.4-diamino benzene sulfonic acid sodium in water, stir 20-25 ℃ of controlled temperature, material dissolution, clarification adds dilute hydrochloric acid regulator solution PH=6-6.5, C%=10-11 in the solution; On the rocksly in solution be cooled to 0-5 ℃, in 1-1.5 hour, add 2.3-two chlorpromazine chlorides, stirring reaction, temperature of reaction 0-5 ℃, reaction PH=6-6.5; 30% hydrochloric acid soln that adds, adjust volume, C%=7, adjust temperature to 5-7 ℃, guarantee to be after congo-red test paper soaks blue at reaction soln, and the KI test paper being little blueness after soaking, is about 30% sodium nitrite solution adding with mass percent concentration with 30-60 minute time, holding temperature 8-10 ℃, reacted 2 hours; Perhaps described step b is: add 1-naphthol-5-sulfonic acid in water, make material dissolution under stirring, clarification, C%=4.9-5 in the solution; Perhaps described step c is: with thionamic acid nitrous acid excessive among the step a eliminated, then this solution followed acid binding agent to join among the step b, and control pH value of solution=7, holding temperature 5-25 ℃, keep PH=7-7.5, reacted 2.5-3 hour.
10, the preparation method of red reactive dye for wool according to claim 5 is characterized in that, the employed acid binding agent of described step a is a sodium bicarbonate; The employed acid binding agent of perhaps described c step is 15% soda ash solution; Carry out the adjustment of intensity with glucose and Sodium sulfate anhydrous.min(99) among the perhaps described step e.
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| CNA2008101541080A CN101481523A (en) | 2008-12-12 | 2008-12-12 | Red reactive dye for fur and preparation thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391674A (en) * | 2011-09-27 | 2012-03-28 | 天津德凯化工股份有限公司 | Garnet active dye |
| CN102433023A (en) * | 2011-09-27 | 2012-05-02 | 天津德凯化工股份有限公司 | Garnet-red reactive dye and preparation method thereof |
| CN102433022A (en) * | 2011-09-27 | 2012-05-02 | 天津德凯化工股份有限公司 | Garnet-red reactive dye and preparation method thereof |
| CN102504590A (en) * | 2011-09-27 | 2012-06-20 | 天津德凯化工股份有限公司 | High-fixation garnet-red active dye and preparation method thereof |
| CN102504578A (en) * | 2011-09-27 | 2012-06-20 | 天津德凯化工股份有限公司 | Single-structure dark-red reactive dye and preparation method thereof |
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| JPS4631153Y1 (en) * | 1967-12-27 | 1971-10-28 | ||
| CN101215425A (en) * | 2008-01-22 | 2008-07-09 | 天津市德凯化工有限公司 | Red reactive dyestuffs and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS4631153Y1 (en) * | 1967-12-27 | 1971-10-28 | ||
| CN101215425A (en) * | 2008-01-22 | 2008-07-09 | 天津市德凯化工有限公司 | Red reactive dyestuffs and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391674A (en) * | 2011-09-27 | 2012-03-28 | 天津德凯化工股份有限公司 | Garnet active dye |
| CN102433023A (en) * | 2011-09-27 | 2012-05-02 | 天津德凯化工股份有限公司 | Garnet-red reactive dye and preparation method thereof |
| CN102433022A (en) * | 2011-09-27 | 2012-05-02 | 天津德凯化工股份有限公司 | Garnet-red reactive dye and preparation method thereof |
| CN102504590A (en) * | 2011-09-27 | 2012-06-20 | 天津德凯化工股份有限公司 | High-fixation garnet-red active dye and preparation method thereof |
| CN102504578A (en) * | 2011-09-27 | 2012-06-20 | 天津德凯化工股份有限公司 | Single-structure dark-red reactive dye and preparation method thereof |
| CN102504578B (en) * | 2011-09-27 | 2016-03-23 | 天津德凯化工股份有限公司 | A kind of single-structure dark-red reactive dye and preparation method thereof |
| CN102504590B (en) * | 2011-09-27 | 2016-03-23 | 天津德凯化工股份有限公司 | A kind of high fixation garnet-red active dye and preparation method thereof |
| CN102433023B (en) * | 2011-09-27 | 2016-06-08 | 天津德凯化工股份有限公司 | A kind of garnet-red reactive dye and preparation method thereof |
| CN102433022B (en) * | 2011-09-27 | 2016-06-08 | 天津德凯化工股份有限公司 | Garnet-red reactive dye and preparation method thereof |
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Application publication date: 20090715 |