CN102516795B - Preparation method of blue dye - Google Patents
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Abstract
The invention relates to a preparation method of a blue dye. The preparation method provided by the invention comprises two times of diazotization reactions; a first diazotization product is mixed with a 1-naphthol-5-sulfonic acid solution and butanone, such that first coupling is carried out; a second diazotization product is subject to a reaction with N,N-diethyl-m-aminophenol, such that a second coupling product is obtained; the first coupling product is subject to a complexation reaction with a chromising reagent, such that a first complexation product is obtained; the first complexation product is mixed with the second coupling product, such that a second complexation reaction is carried out, and the asymmetric 1:2 blue dye represented by a formula I is obtained. According to the preparation method provided by the invention, butanone is used as a protecting agent for the diazotization product in the first coupling reaction, such that the diazotization product is more stable, the reaction between the diazotization product and 1-naphthol-5-sulfonic acid is more sufficient, the yield of the first coupling product is improved, and COD content in sewage is reduced. The formula I is presented below.
Description
Technical field
The present invention relates to fabric finishing technical field, relate in particular to a kind of preparation method of blue dyes.
Background technology
Matching stain (Acid Dyes) is the dyestuff that a class dyes in acidic medium.The large multipotency of matching stain is water-soluble, bright in colour, chromatogram is complete.Be mainly used in the dyeing such as wool, silk and polyamide fibre, also can be used for the aspects such as leather, paper, ink.To the general non-coloring power of cellulosic fibre.And in matching stain, the performance of acidic complex dye is the most excellent, apply also extensive.Acidic complex dye is to be formed by metal complexes such as matching stain and chromium, cobalts.Water soluble, it dyes product sun-proof, light fastness is good.Its dye matrix is similar with acid mordant dye, but when preparing dyestuff, atoms metal is introduced in Azo dye, and atoms metal is 1: 1 with dye molecule ratio, therefore claim again 1: 1 metallized dye.During dyeing, do not need with mordant, to process again.GR (being C.I. acid yellow 99) as yellow in acid complexing.
At present, acid metal chromium complex dyestuff has two kinds according to complexing classification: (1) one step complexometry: the disposable metal complex that carries out of all monoazo-dyes, randomness due to molecular reaction, easily generate a large amount of byproducts, the main content of product is on the low side, has a strong impact on the application performance of dyestuff.(2) two step complexometries: in all monoazo-dyes, preferential certain component wherein of selecting is carried out a complexing, forms 1: 1 complex compound, then carries out secondary complexing with remaining monoazo-dyes, generates 1: 2 metallized dye.
In acidic complex dye, working as that added value is the highest belongs to asymmetric 1: 2 metallized dye---You Lite (Neutral) dyestuff, because its good dyeing behavior, excellent fastness, outstanding compatibleness are subject to the favor in market.
You Lite dyestuff has suitable solubleness, meets the requirement of short liquor dyeing; Coloured light is more bright-coloured; After mixed aid, can under the condition of pH value=5, dye, reduce the damage to fibers such as wools in dyeing course; Dyeing behavior is good, and particularly crabbing fastness is better, can adapt to the requirement of spinning dyeing; Complex stability is good.During dyeing, fabric heavy metal content is low, meets the requirement of environmental protection; The compatbility of dyestuff is good, with the dyeing of the blending such as neutral dye, weak acid dye, reactive dye for wool, stable performance, circulation ratio good level-dyeing property; Can be widely used in colored leather, be the primary categories of water-soluble leather dyestuff; Dye structure itself is non-carcinogenic dyestuff, non-acute toxicity dyestuff, nonallergic dyestuff; The synthetic raw material used of dyestuff is not the carcinogenic aromatic amine raw material of German Government and European Community's regulation; Adopt two step complexing techniques, can fully guarantee that heavy metal few in dye product is remaining, and then guarantee that the residual quantity of textiles heavy metal does not exceed standard.You Lite dyestuff is complexing stable form dyestuff, and the decomposition that can not be damaged in the application process of dyestuff, discharges carcinogenic aromatic amine and heavy metal.
The preparation method of asymmetric 1: 2 metallized dye is mainly two step complexometries at present, according to the difference of production technique, be divided into following two kinds of methods: (1) borrows the production technique of 1: 1 metallized dye, adopt the method for formic acid and chromic formate to carry out acid complexing, then by generating complexing in 1: 2 with the second azoic dyestuff under 1: the 1 metallized dye alkaline condition generating.(2) adopt organic solvent method as added the acid complexing of potassium bichromate in ethylene glycol solvent, generate 1: 1 metallized dye, then by generating complexing in 1: 2 with the second azoic dyestuff under 1: the 1 metallized dye alkaline condition generating.(3) in acidic medium, Whitfield's ointment chromium, chromic tartrate complexing, then by generating complexing in 1: 2 with the second azoic dyestuff under 1: the 1 metallized dye alkaline condition generating.
But still there is certain problem in two step complexometries of prior art: one time diazonium protective material adopts naphthene sulfonic acid, and coupling yield is low, produces the waste water that COD is higher after press filtration.A complexing does not detect a coupling yield, has added the chromaking agent that substantially exceeds theoretical consumption, has caused larger wastage of material; After press filtration, produce the higher waste water of chromium content, caused environmental pollution.Prior art, for guaranteeing quality product, has been taked multistep press filtration, has produced on the one hand the waste water of larger supersalinity; Intensity and the energy consumption of hand labor have been strengthened on the other hand.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of the first coupled reaction productive rate high, and hazardous emission is few, the preparation method of the blue dyes that raw material consumption is few.
In order to solve above technical problem, the invention provides the preparation method of the blue dyes shown in a kind of formula I, comprising:
A) by 2-Amino-5-nitrophenol, hydrochloric acid and nitrous solution in the abundant middle mixing of frozen water, carry out diazotization reaction for the first time, obtain the first diazonium product;
B) the first diazonium product, butanone, the 1-naphthol-5-sulfonic acid solution that step a) are obtained, carry out coupled reaction for the first time, obtains the first coupling product;
C) by 2-Amino-5-nitrophenol, hydrochloric acid, Sodium Nitrite is blended in ice-water bath, uses potassiumiodide colour developing, carries out diazotization reaction for the second time, obtains the second diazonium product;
D), by N, the alkaline solution of the m-hydroxyanilines of N-diethyl mixes with the second diazonium product, carries out coupled reaction for the second time, obtains the second coupling product;
E), by the first coupling product, under acidic conditions, with basic chromium sulfate, Whitfield's ointment, complexing is for the first time carried out in sodium formiate mixing, obtains the first complexing product;
F) the first complex compound is mixed and carries out complexing for the second time with the second conjugates, product is through saltouing, press filtration.Obtain the blue dyes shown in formula I.
Formula I
Preferably, step a) is specially:
A1) in water, add 2-Amino-5-nitrophenol, with liquid caustic soda, adjust pH=12.5-13, stir 30～60min, entirely molten to 2-Amino-5-nitrophenol;
A2) solution step a) being obtained and hydrochloric acid, cool to 0-5 ℃, at this temperature, adds sodium nitrite solution, carries out diazotization reaction for the first time in ice-water bath, obtains the first diazonium product.
Preferably, described 1-naphthol-5-sulfonic acid solution is prepared by the following method:
By 1-naphthol-5-sulfonic acid in the water of 25-30 ℃, dissolve, suction strainer, filtrate is cooled to 10～15 ℃, obtains 1-naphthol-5-sulfonic acid solution.
Preferably, described N, a N-diethyl-hydroxyanilines solution is prepared by the following method:
Under stirring, liquid caustic soda is heated to 65-70 ℃, by the N of fusing, a N-diethyl-hydroxyanilines mixes with described liquid caustic soda; Insulated and stirred is to described N, and a N-diethyl-hydroxyanilines all dissolves suction strainer.Filtrate is down to 10-15 ℃, obtains N, a N-diethyl-hydroxyanilines solution.
Preferably, step b) be specially:
B1) the first coupling product and thionamic acid being destroyed to excessive Sodium Nitrite mixes;
B2) by butanone and step b1) mixture that obtains mixes, described 1-naphthol-5-sulfonic acid solution, at 10～15 ℃, adjusting pH is 7.7～8.0, insulation reaction, to terminal, steams after butanone, completes a coupling.
Preferably, step c) be specially:
C1) 2-Amino-5-nitrophenol and liquid caustic soda are blended in water, regulating pH value is 12.5～13, treats that 2-Amino-5-nitrophenol all dissolves;
C2) at step c1) add hydrochloric acid in 2-Amino-5-nitrophenol solution, cool to 0-5 ℃, then add Sodium Nitrite, diazotization reaction is for the second time carried out in insulation, obtains the second diazonium product.
Preferably, steps d) be specially:
D1) described the second diazonium product being destroyed to excessive Sodium Nitrite with thionamic acid mixes;
D2) by steps d 1) mixture and the described N that obtain, the alkaline solution of the m-hydroxyanilines of N-diethyl mixes, and carries out coupled reaction for the second time, obtains the second coupling product.
Preferably, step e) be specially:
E1) the first coupling product is adjusted to pH=1.5-2.0 with hydrochloric acid;
E2) basic chromium sulfate, Whitfield's ointment, sodium formiate being added to step e1) in the first coupling product of obtaining, sealing is warmed up to 140-145 ℃, carries out complex reaction for the first time, obtains the first complexing product.
Preferably, step f) be specially:
The first complexing product is mixed with the second coupling product, is warming up to 85-90 ℃, adjust pH=10.0-10.5, insulation reaction, TLC plate endpoint detection, qualified after, adjust pH=7.5-8.0, cool to 65-70 ℃, add refined salt to saltout, press filtration.Obtain blue asymmetric chromium complex dyestuff.
Preferably, described chromaking reagent is: one or more in basic chromium sulfate, potassium bichromate, Whitfield's ointment chromium, chromic tartrate and chromic formate.
Preparation method provided by the invention comprises diazotization reaction twice, then the first diazonium product is mixed and carries out coupling for the first time with 1-naphthol-5-sulfonic acid solution and butanone, then by the second diazonium product and N, a N-diethyl-hydroxyanilines reaction obtains the second coupling product, the first coupling product and chromaking reagent are carried out to complex reaction, obtain the first complexing product, described the first complexing product is mixed with described the second coupling product, carry out complex reaction for the second time, obtain asymmetric 1: 2 blue dyes.Preparation method provided by the invention, while using butanone as coupling for the first time, the protective material of diazonium product, makes diazonium product more stable; carry out more thorough that react with 1-naphthol-5-sulfonic acid; the first coupling product productive rate is improved, reduce the content of COD in waste water, reduced environmental pollution.Before complex reaction for the first time, can detect in addition the purity of the first coupling product, by theoretical amount, add chromium, after complexing, can directly carry out complex reaction for the second time for the first time, suction filtration repeatedly, raw material usage quantity is few.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these are described is the restriction for further illustrating the features and advantages of the present invention rather than patent of the present invention being required.
The preparation method who the invention provides the blue dyes shown in a kind of formula I, comprising:
A) by 2-Amino-5-nitrophenol, hydrochloric acid and nitrous solution in the abundant middle mixing of frozen water, carry out diazotization reaction for the first time, obtain the first diazonium product;
B) the first diazonium product, butanone, the 1-naphthol-5-sulfonic acid solution that step a) are obtained, carry out coupled reaction for the first time, obtains the first coupling product;
C) by 2-Amino-5-nitrophenol, hydrochloric acid, Sodium Nitrite is blended in ice-water bath, uses potassiumiodide colour developing, carries out diazotization reaction for the second time, obtains the second diazonium product;
D), by N, the alkaline solution of the m-hydroxyanilines of N-diethyl mixes with the second diazonium product, carries out coupled reaction for the second time, obtains the second coupling product;
E), by the first coupling product, under acidic conditions, with basic chromium sulfate, Whitfield's ointment, complexing is for the first time carried out in sodium formiate mixing, obtains the first complexing product;
F) the first complex compound is mixed and carries out complexing for the second time with the second conjugates, product is through saltouing, press filtration.Obtain the blue dyes shown in formula I.
Formula I
Preparation method provided by the invention, first carry out twice diazotization processing, 2-Amino-5-nitrophenol is dissolved under alkaline condition, and under acidic conditions, carry out diazotization reaction with nitrite, obtain diazonium product, described nitrite is preferably Sodium Nitrite, and wherein diazotization reaction is specially for the first time:
A1) in water, add 2-Amino-5-nitrophenol, with liquid caustic soda, adjust pH=12.5-13, stir 30～60min, entirely molten to 2-Amino-5-nitrophenol;
A2) solution step a) being obtained and hydrochloric acid, cool to 0-5 ℃, at this temperature, adds sodium nitrite solution, carries out diazotization reaction for the first time in ice-water bath, obtains the first diazonium product.According to the present invention, the time of described stirring is preferably 40min.
Specifically reaction equation is as shown in Equation 1:
Formula 1.
The first diazonium product is mixed with butanone, and then with 1-naphthol-5-sulfonic acid, coupled reaction for the first time occurs.Butanone can be protected diazonium product, makes it stable, with carry out more thorough that react of 1-naphthol-5-sulfonic acid, the first coupling product productive rate is improved, and according to the present invention, described coupled reaction is for the first time specially:
B1) the first coupling product and thionamic acid being destroyed to excessive Sodium Nitrite mixes;
B2) by butanone and step b1) mixture that obtains mixes, described 1-naphthol-5-sulfonic acid solution, at 10～15 ℃, adjusting pH is 7.7～8.0, insulation reaction, to terminal, steams after butanone, completes a coupling.
Specifically reaction equation is as shown in Equation 2:
Formula 2.
Then carry out diazotization reaction for the second time, process is specially:
C1) 2-Amino-5-nitrophenol and liquid caustic soda are blended in water, regulating pH value is 12.5～13, treats that 2-Amino-5-nitrophenol all dissolves;
C2) at step c1) add hydrochloric acid in 2-Amino-5-nitrophenol solution, cool to 0-5 ℃, then add Sodium Nitrite, diazotization reaction is for the second time carried out in insulation, obtains the second diazonium product.Described Sodium Nitrite preferably divides and adds for 30 minutes,
More preferably described the second diazonium product is used to potassiumiodide colour developing, regulate pH≤2, in 0-5 ℃ of insulation 0.5～2h, before carrying out coupling for the second time, add thionamic acid to destroy excessive Sodium Nitrite.
Specifically reaction equation is as shown in Equation 3:
Formula 3.
Then carry out coupling for the second time: by the second diazonium product and N, the alkaline solution of the m-hydroxyanilines of N-diethyl mixes, and at 10-15 ℃, with liquid caustic soda, adjusts pH=11, and insulation reaction is to terminal.Complete secondary coupling.According to coupled reaction for the second time of the present invention, be specially:
D1) described the second diazonium product being destroyed to excessive Sodium Nitrite with thionamic acid mixes;
D2) by steps d 1) mixture and the described N that obtain, the alkaline solution of the m-hydroxyanilines of N-diethyl mixes, and carries out coupled reaction for the second time, obtains the second coupling product.
Specifically reaction equation is as shown in Equation 4:
Formula 4.
Coupling product and chromaking reagent mix, carry out complex reaction for the first time for the first time.Described chromaking reagent is preferably: one or more in basic chromium sulfate, potassium bichromate, Whitfield's ointment chromium, chromic tartrate and chromic formate, more preferably basic chromium sulfate.According to complex reaction for the first time of the present invention, be specially:
E1) the first coupling product is adjusted to pH=1.5-2.0 with hydrochloric acid;
E2) basic chromium sulfate, Whitfield's ointment, sodium formiate being added to step e1) in the first coupling product of obtaining, sealing is warmed up to 140-145 ℃, carries out complex reaction for the first time, obtains the first complexing product.
The volume and the productive rate that it should be noted that detection the first coupling product of complexing for the first time.Fully size mixing, metering volume, analyzes content; Add basic chromium sulfate, Whitfield's ointment, sodium formiate, after sealing is warmed up to 140-145 ℃, preferred insulation reaction is 3 hours, cools to 60 ℃, filters, and filter cake washes with water, completes complex reaction for the first time.
The concrete reaction equation of complex reaction is for the first time as shown in Equation 5:
Formula 5
Finally the first complexing product is mixed with the second coupling product, asymmetric 1: 2 metallized dye shown in preparation formula I, is specially:
The first complexing product is mixed with the second coupling product, is warming up to 85-90 ℃, adjust pH=10.0-10.5, insulation reaction, TLC plate endpoint detection, qualified after, adjust pH=7.5-8.0, cool to 65-70 ℃, add refined salt to saltout, press filtration.Obtain blue asymmetric chromium complex dyestuff.
Specifically reaction equation is as shown in Equation 6:
Formula 6
Be below the specific embodiment of the invention, elaborate the present invention program:
Embodiment 1
A, 1-naphthol-5-sulfonic acid, N, the dissolving suction strainer of a N-diethyl-hydroxyanilines
In reactor, add 2040L water, temperature adjustment to 25 ℃, adds 352.2Kg 1-naphthol-5-sulfonic acid under stirring, stirs 40min to complete molten suction strainer, filtrate drop to 10-15 ℃ standby.
In dissolving pan, add water, start and stir, add 117Kg liquid caustic soda, temperature adjustment, to 65-70 ℃, is opened vacuum and is sucked the N having melted, a N-diethyl-hydroxyanilines, insulated and stirred one hour, complete molten suction strainer.Filtrate will arrive 10 ℃ standby.
B, a diazotization
In L reactor, add 680L water, 235.62Kg 2-Amino-5-nitrophenol, with liquid caustic soda, adjust pH=12.5-13, stir entirely molten, add 153Kg hydrochloric acid, cool to 0-5 ℃, at this temperature, with within 30 minutes, adding 105.4Kg nitrous solution, use during this time ice temperature control, add, continue at 0-5 ℃ of insulation one hour, before coupling, add appropriate thionamic acid to destroy excessive Sodium Nitrite.Below 10 degrees Celsius, with thin liquid alkali (12%-15%), adjust pH=4.0-4.5, proceed to coupling pot for coupling
C, a coupling
In a diazo liquid, add 1455Kg butanone, cool to 5 ℃, receive 1-naphthol-5-sulfonic acid filtrate, at 10-15 ℃, adjust pH=7.7-8.0, check terminal, after terminal, stir again 4 hours.Intensification steams after butanone, cools to 40 ℃, proceeds to complexing pot one time.
D, secondary diazotization
In reactor, add water 1700L, 235.62Kg 2-Amino-5-nitrophenol, 159.8L liquid caustic soda, entirely molten, add hydrochloric acid, cool to 0-5 ℃, add 476L Sodium Nitrite with 30 minutes, add in 0-5 ℃ of insulation one hour, before coupling, add thionamic acid to destroy excessive Sodium Nitrite.
E, secondary coupling
By N, the m-hydroxyanilines filtrate of N-diethyl joins in diazo liquid slowly, and 30min adds, and at 10-15 ℃, with liquid caustic soda, adjusts pH=10.9-11.1, and insulation reaction is to terminal.Terminal, to rear insulation two hours, is treated two complexings.
F, a complexing
In reactor, add conjugates one time, fully size mixing, metering volume, sampling send quality control portion to analyze content, with hydrochloric acid, adjusts pH=1.5-2.0, adds basic chromium sulfate, Whitfield's ointment, sodium formiate, metering volume, sealing is warmed up to 140-145 ℃, insulation reaction 3 hours, cool to 60 ℃, arm-tie layer after terminal, suction strainer, filter cake is treated two complexings with 1700L washing.
G, secondary complexing
In reactor, add complex compound one time, secondary conjugates, is warming up to 85-90 ℃, adjusts pH=10.0-10.5, and TLC judge terminal, qualified after, tune pH=7.5-8.0, cools to 65-70 ℃, adds refined salt to saltout, press filtration obtains dyestuff.
Above a kind of blue dyes provided by the invention and preparation method thereof is described in detail; having applied specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (4)
1. a preparation method for the blue dyes shown in formula I, is characterized in that, comprising:
A) 2-Amino-5-nitrophenol, hydrochloric acid and nitrite solution are mixed in ice-water bath, carry out diazotization reaction for the first time, obtain the first diazonium product;
Step a) is specially:
A1) in water, add 2-Amino-5-nitrophenol, with liquid caustic soda, adjust pH=12.5-13.0, stir 30～60min, entirely molten to 2-Amino-5-nitrophenol;
A2) by step a1) solution and the hydrochloric acid that obtain, cool to 0-5 ℃, at this temperature, add sodium nitrite solution, in ice-water bath, carry out diazotization reaction for the first time, obtain the first diazonium product;
B) the first diazonium product, butanone, the 1-naphthol-5-sulfonic acid solution that step a) are obtained, carry out coupled reaction for the first time, obtains the first coupling product;
Step b) is specially:
B1) the first diazonium product is mixed with thionamic acid, destroy excessive Sodium Nitrite;
B2) by butanone and step b1) mixture that obtains mixes, described 1-naphthol-5-sulfonic acid solution, at 10～15 ℃, adjusting pH is 7.7～8.0, insulation reaction, to terminal, steams after butanone, completes a coupling;
C) by 2-Amino-5-nitrophenol, hydrochloric acid, Sodium Nitrite is blended in ice-water bath, uses potassiumiodide colour developing, carries out diazotization reaction for the second time, obtains the second diazonium product;
Step c) is specially:
C1) 2-Amino-5-nitrophenol and liquid caustic soda are blended in water, regulating pH value is 12.5～13.0, treats that 2-Amino-5-nitrophenol all dissolves;
C2) at step c1) add hydrochloric acid in 2-Amino-5-nitrophenol solution, cool to 0-5 ℃, then add Sodium Nitrite, diazotization reaction is for the second time carried out in insulation, obtains the second diazonium product;
D), by N, the alkaline solution of the m-hydroxyanilines of N-diethyl mixes with the second diazonium product, carries out coupled reaction for the second time, obtains the second coupling product;
E), by the first coupling product, under acidic conditions, with basic chromium sulfate, Whitfield's ointment, complexing is for the first time carried out in sodium formiate mixing, obtains the first complexing product;
Step e) is specially:
E1) the first coupling product is adjusted to pH=1.5-2.0 with hydrochloric acid;
E2) basic chromium sulfate, Whitfield's ointment, sodium formiate being added to step e1) in the first coupling product of obtaining, sealing is warmed up to 140-145 ℃, carries out complex reaction for the first time, obtains the first complexing product;
F) the first complex compound is mixed and carries out complexing for the second time with the second coupling product, product is through saltouing, and press filtration, obtains the blue dyes shown in formula I;
Step f) is specially:
The first complexing product is mixed with the second coupling product, be warming up to 85-90 ℃, adjust pH=10.0-10.5, insulation reaction, TLC plate endpoint detection, qualified after, adjust pH=7.5-8.0, cool to 65-70 ℃, add refined salt to saltout, press filtration, obtains blue asymmetric chromium complex dyestuff;
Formula I.
2. preparation method according to claim 1, is characterized in that, described 1-naphthol-5-sulfonic acid solution is prepared by the following method:
By 1-naphthol-5-sulfonic acid in the water of 25-30 ℃, dissolve, suction strainer, filtrate is cooled to 10～15 ℃, obtains 1-naphthol-5-sulfonic acid solution.
3. preparation method according to claim 1, is characterized in that, described N, and a N-diethyl-hydroxyanilines solution is prepared by the following method:
Under stirring, liquid caustic soda is heated to 65-70 ℃, by the N of fusing, a N-diethyl-hydroxyanilines mixes with described liquid caustic soda; Insulated and stirred is to described N, and a N-diethyl-hydroxyanilines all dissolves suction strainer, and filtrate is down to 10-15 ℃, obtains N, a N-diethyl-hydroxyanilines solution.
4. preparation method according to claim 1, is characterized in that, step d) is specially:
D1) described the second diazonium product is mixed with thionamic acid, destroy excessive Sodium Nitrite;
D2) by steps d 1) mixture and the described N that obtain, the alkaline solution of the m-hydroxyanilines of N-diethyl mixes, and carries out coupled reaction for the second time, obtains the second coupling product.
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| CN105623300B (en) * | 2016-01-05 | 2017-08-01 | 湖北省纬庆高分子科技有限公司 | A kind of preparation method of complex dyestuff |
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