CN103289431A - Method for preparing reactive brilliant blue 3G for wool - Google Patents
Method for preparing reactive brilliant blue 3G for wool Download PDFInfo
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- CN103289431A CN103289431A CN2012100465137A CN201210046513A CN103289431A CN 103289431 A CN103289431 A CN 103289431A CN 2012100465137 A CN2012100465137 A CN 2012100465137A CN 201210046513 A CN201210046513 A CN 201210046513A CN 103289431 A CN103289431 A CN 103289431A
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Abstract
The invention provides a method for preparing reactive brilliant blue 3G for wool. The method comprises the following steps of: (1) condensing bromamine acid and p-amine acetanilide under the action of a catalyst, and acidifying to obtain a condensation product; (2) sulfonating the condensation product by using fuming sulfuric acid, and performing basic hydrolysis to remove acetyl; and (3) condensing a hydrolysis product with 2,3-dibromo propionyl chloride, and performing debromination to prepare a reactive brilliant blue 3G dye. The preparation method provided by the invention is low in cost, energy consumption and pollution, and is suitable for industrial large-scale production. Various application performance indexes of the reactive brilliant blue 3G for wool, which is obtained by the preparation method provided by the invention, reach or exceed those of products of foreign companies.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind of reactive dyestuffs preparation method's research, relate to a kind of method that hair is used reactive brilliant bule 3G for preparing particularly.
Background technology
Ciba company began to release Lanasol series reactive dye for wool in 1966.In Lanasol series reactive dyestuffs, Lanasol Blue 3G is one of them blue kind, is called hair on the domestic market and uses reactive brilliant bule 3G, and structural formula is as follows:
Hair can be used for dyeing and the stamp of protein fibre material with gorgeous blue 3G reactive dyestuffs, and for example dyeing and the stamp of fibers such as wool, cashmere, silk also can be used for diffusing hair, wool top, yarn, carpet, through the fabric of shrink proof finish and dyeing and the stamp of woven fabrics.Hair after the dyeing of fibers such as wool, silk, presents gorgeous blueness with reactive brilliant bule 3G dyestuff, has high degree of fixation and excellent light fastness and dyefastness.
The preparation method of relevant Lanasol Blue 3G has introduction in patent CH489581, be starting raw material through oversulfonate, with 2 with 1-amino-4-(4 '-amino aniline)-anthraquinone-2-sulfonic acid (as shown in the formula II), 3-two bromo propionyl chloro condensations, perhaps earlier with 2,3-two bromo propionyl chloro condensations, sulfonation again, debrominate then, saltouing obtains product Lanasol Blue 3G.
Poland Patent PL40811 discloses the synthetic method of a kind of 1-amino-4-(4 '-amino aniline)-anthraquinone-2-sulfonic acid: bromamine acid and Ursol D carry out condensation reaction and obtain, and are reflected under the nitrogen protection and carry out.This method long reaction time, foreign pigment is many, treating process is complicated (multistep is refining, for example decolouring, step such as saltout), and the amount of getting is low; While prior preparation method used 2,3-two bromo propionyl chloros need be dissolved in organic solvent (for example acetone) earlier, last debrominate liquid all needs to saltout and just can be met the purpose product that printing and dyeing require, operation has lengthened reaction time, has increased labour intensity and energy consumption like this, and coloured filtrate is brought a large amount of pollutions to environment simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of hair for preparing with the method for reactive brilliant bule 3G, to overcome the big and problem of environmental pollution of length reaction time, labour intensity that existing preparation method exists.By a large amount of research, the applicant develops a suitable suitability for industrialized production, the simple operational path of aftertreatment, has determined appropriate processing condition in each reactions steps, thereby has finished the present invention, has realized purpose of the present invention.
Technical scheme of the present invention is as follows:
A kind of mao method with reactive brilliant bule 3G for preparing, may further comprise the steps: 1) bromamine acid and para aminoacet anilide carry out condensation under catalyst action, obtain condensation product after the acidification; 2) condenses oleum sulfonation, alkaline hydrolysis deacetylate again; 3) hydrolysate and 2,3-, two bromo propionyl chloro condensations, debrominate makes the gorgeous blue 3G of dye activity again.Preparation flow is expressed as follows with equation:
Appropriate processing condition of the present invention is as follows:
1) bromamine acid and para aminoacet anilide carry out under catalyst action in the reactions steps of condensation, and described catalyzer is selected from copper sulfate and tin protochloride.The add-on of two kinds of catalyzer (in mole) is respectively 5～10% of bromamine acid.The molar ratio of bromamine acid and para aminoacet anilide is 1: 1～2.5, and condensation temp is 40～100 ℃, pH value 8～12; Further preferred molar ratio is 1: 1～1.3, and condensation temp is 60～90 ℃, pH value 9～11.
Different from the past is the operating method (needing in batches, for example add in three batches catalyzer when the condensation reaction) of the anthraquinone dyes of raw material production with bromamine acid, and the catalyzer of above-mentioned condensation reaction can disposablely add.So both handled easily was time saving and energy saving again.
After condensation reaction was finished, acidification condensation product, filtration, filtration cakes torrefaction were standby.Suitable acidulated condition: pH value 0～3,5～80 ℃ of filtration temperatures; Preferred acidulated condition: pH value 1～2,20～50 ℃ of filtration temperatures.
When 2) Gan Zao condenses carries out sulfonation and hydrolysis reaction, at first under 0～5 ℃, condenses added in batches 3%～25% (free SO
3Content) in the oleum, free SO in condenses and the oleum
3Mol ratio be 1: 1.5～3.The control temperature of reaction is at 0～60 ℃; In alkaline aqueous solution (for example aqueous sodium hydroxide solution), be hydrolyzed deacetylate, 40～100 ℃ of hydrolysising reacting temperatures then.
Preferred sulfonation reaction condition is 25～40 ℃ of temperature, oleum concentration 7%～15%; Preferred hydrolysis reaction condition is 70～100 ℃ of temperature.
3) hydrolysate and 2,3-, two bromo propionyl chloros carry out condensation reaction when (also claiming the secondary condensation), and reaction conditions preferably reinforced mol ratio is 1: 1～1.5, and condensation temp is-5～25 ℃, pH value 3～9; Further preferred molar ratio is 1: 1～1.3, and condensation temp is-5～10 ℃, pH value 5～8.This step operation is different with well-established law, and 2,3-, two bromo propionyl chloros directly are added in the hydrolysate, this step is reacted not only lower consumption, but also saves time.
Regulate pH value to 8～11 of two condensation reaction solution that above-mentioned secondary condensation obtains, carry out debromination in 20～60 ℃, obtain the dye solution of purpose product; Further preferred reaction conditions is 30～50 ℃ of debromination temperature, pH=8～10.
Obtain the dye solution that hair is used reactive brilliant bule 3G according to preparation method provided by the invention, directly spraying drying obtains product.This dye solution with the prior art report needs to compare through the refining scheme that just can obtain product of oversalting, and preparation method provided by the invention is simple to operate, and is time saving and energy saving, energy-conservation.
Above-mentionedly respectively go on foot operation and reinforced proportioning, and the span of control that respectively goes on foot temperature of reaction and pH value is the key condition of target compound in the preparation this patent.In triturating, find: at first, when the feeding quantity of two kinds of catalyzer and para aminoacet anilide is too high, though do not influence must measuring and quality (namely can satisfy the requirement of application performance) of product, raw material consumption increases and aftertreatment loaded down with trivial details (for example needing to reclaim raw material etc.); And reduce the feeding quantity of para aminoacet anilide, a condenses must measure reduction, product must be measured and must decrease.Secondly, bromamine acid and para aminoacet anilide setting-up point reduce, and then the reaction times prolongs, increases energy consumption; And temperature of reaction is too high, though the reaction times shortens to some extent not obvious (0.5～1 hour), increases energy consumption equally.The 3rd, the pH value during acidifying is too low, and not only acid consumption is big, and bad operation; Simultaneously, the pH value is low, when filtration temperature is too high, and material is separated out not exclusively, and product must be measured low.The 4th, during sulfonation reaction, the concentration of oleum is low then to be influenced speed of response or reacts incomplete, and the spent acid of generation is many, is unfavorable for aftertreatment; Excessive concentration, the by-product of product increases, and the energy consumption of cooling strengthens, and is unfavorable for aftertreatment (for example product needed is refining) equally.The 5th, temperature is low excessively during debromination, and reaction needs to carry out under high pH value; And pH is too high, can introduce a large amount of inorganic salt (for example sodium-chlor), causes the staining power of dyestuff to reduce.Therefore, determine to be fit to commercial scale production and to satisfy this product be very necessary to low cost, less energy-consumption, the optimum reaction conditions of hanging down the pollution demand.
Compare the colour fastness that shows same high dye uptake and degree of fixation and excellence with preparation method of the present invention synthesized hair with the dyestuff Lanasol Blue 3G of reactive brilliant bule 3G product and present U.S. Huntsman company (former Ciba company); But lifting force is apparently higher than Lanasol Blue 3G, and the every colour fastness on wool fabric all meets or exceeds Lanasol Blue 3G level.For example, adopting the resulting dyestuff of preparation method of the present invention is 0.5%, 1%, 2%, 4%, 5%, 6% o'clock at dye level, its Integ value exceeds 0.2742,0.5210,2.4298,0.2864,0.4889 and 2.5934 than Lanasol Blue 3G respectively under equal dye level, and degree of fixation is higher than standard 1.08%.So the hair provided by the invention preparation method of reactive brilliant bule 3G, satisfied market to low cost, less energy-consumption, the low needs that pollute DYE PRODUCTION, improved the competitive power in market, make this dyestuff have more wide Commercial Prospect.
Embodiment
Following examples are used for further specifying the present invention.The umber that wherein relates to is parts by weight, except the solution of indicating concentration especially, all is converted to pure product metering; Concentration unit is concentration expressed in percentage by weight.The preparation hair used intermediate bromamine acid of reactive brilliant bule 3G dyestuff, para aminoacet anilide, 2,3-two bromo propionyl chloros and other raw materials all have commercially available.The method that the dyestuff application testing adopts is as well known to those skilled in the art public.
Dyestuff prepares embodiment
Embodiment 1
The condensation reaction of a, bromamine acid and para aminoacet anilide
In three mouthfuls of reaction flasks, add 40 parts in 1.68 parts of sodium bicarbonates, 1.06 parts in yellow soda ash and water, stirring and dissolving.After treating to dissolve fully, add 0.125 part of 4.04 parts of bromamine acids, 1.8 parts of para aminoacet anilides, 0.125 part in copper sulfate and tin protochloride successively, heat up 70～80 ℃, stirring reaction 4 hours, thin-layer chromatography or HPLC detect the bromamine acid reaction of disappearance and finish.Be down to room temperature and filter, filter cake mixes with 40 parts of water, transfers pH=1.5～2.0 with 30% hydrochloric acid, stirs, and room temperature is filtered, and obtains 4.5 parts of condensess behind the filtration cakes torrefaction, and is standby.
B, sulfonation reaction
Add 20 part of 8～10% oleum in three mouthfuls of reaction flasks of drying, 0～5 ℃ of frozen water cooling adds the condenses that obtains in (a) in batches, behind reinforced the finishing, is warming up to 25～35 ℃ of reactions 1.5～2 hours, and condenses reacts completely, and reaction finishes.Slowly pour in the mixing solutions of 60 portions of frozen water, constantly stir.The solid collected by filtration precipitate changes in the beaker then, adds 40 parts of water, transfers to neutral stand-by with sodium hydroxide.
C, hydrolysis reaction
The sulfonation aqueous solution that (b) obtained is transferred in three mouthfuls of reaction flasks, adds 1 part of solid sodium hydroxide, is warming up to 90～100 ℃ of reactions about hour, and HPLC detects to the sulfonated bodies disappearance, and reaction finishes.Reaction solution is down to room temperature, and is extremely neutral with 30% hydrochloric acid adjust pH.Add 6 parts in sodium-chlor, saltout.Filter, filter cake is dissolved in 40 parts of water, and is standby.
D, two condensation reactions
The hydrolyzate solution that (c) obtained is transferred in three mouthfuls of reaction flasks, adds 1.06 parts in yellow soda ash, stirring and dissolving, and frozen water is cooled to 0～5 ℃, slowly drips 2.2 parts of 2,3-, two bromo propionyl chloros.Dropwise, continue to react and detect hydrolyzate to HPLC and disappear and be reaction end.
E, debromination
Two condensation reaction solution that (d) obtained are warming up to 40～50 ℃, transfer pH=8～10 with sodium hydroxide solution, and HPLC detects the disappearance of two condensess and is reaction end.After reaction finished, the direct spraying drying of feed liquid got 8.7 parts of target product hair reactive brilliant bule 3G.
Embodiment 2
Repeat operating process and processing condition described in the embodiment 1, just in the step (a) of embodiment 1, change the add-on of copper sulfate and tin protochloride into 0.25 part separately, finally obtain 8.5 parts hair reactive brilliant bule 3G.
Embodiment 3
Repeat operating process and processing condition described in the embodiment 1, just in the step (a) of embodiment 1, the para aminoacet anilide add-on changes 1.5 parts into, obtains 3.6 parts behind the primary condensation filtration cakes torrefaction, finally obtains 7 parts hair reactive brilliant bule 3G.
Embodiment 4
Repeat operating process and processing condition described in the embodiment 1, just in the step (a) of embodiment 1, the para aminoacet anilide add-on changes 3.75 parts into, obtains 4.8 parts behind the primary condensation filtration cakes torrefaction, finally obtains 8.9 parts hair reactive brilliant bule 3G.
Embodiment 5
Repeat operating process and processing condition described in the embodiment 1, just in the step (a) of embodiment 1, condensation temp is 70 ℃, and condensation reaction time is 8 hours, finally obtains 8.5 parts hair reactive brilliant bule 3G.
Embodiment 6
Repeat operating process and processing condition described in the embodiment 1, just in the step (a) of embodiment 1, condensation temp is 100 ℃, and condensation reaction time is 3 hours, finally obtains 8.5 parts hair reactive brilliant bule 3G.
Embodiment 7
Repeat operating process and processing condition described in the embodiment 1, just in the step (a) of embodiment 1, transfer pH=0 with 30% hydrochloric acid, filtration temperature is 20 ℃, finally obtains 8.7 parts hair reactive brilliant bule 3G.
Embodiment 8
Repeat operating process and processing condition described in the embodiment 1, just in the step (a) of embodiment 1, transferring pH with 30% hydrochloric acid is 3.0, and filtration temperature is 60 ℃, obtains 3.2 parts behind the primary condensation filtration cakes torrefaction, finally obtains 6.6 parts hair reactive brilliant bule 3G.
Embodiment 9
Repeat operating process and processing condition described in the embodiment 1, just in the step (b) of embodiment 1, add 35 parts of 5% oleums; Finally obtain 8.0 parts hair reactive brilliant bule 3G.
Embodiment 10
Repeat operating process and processing condition described in the embodiment 1, just in the step (b) of embodiment 1, the sulfonation reaction temperature changes 10 ℃ into, and sulfonation reaction 10 hours finally obtains 8.5 parts hair reactive brilliant bule 3G.
When the sulfonation reaction temperature changed 0 ℃ into, the sulfonation reaction time surpassed 20 hours and finishes.
Embodiment 11
Repeat operating process and processing condition described in the embodiment 1, just in the step (b) of embodiment 1,45 ℃ of sulfonation temperatures, finally obtain 7.6 parts hair reactive brilliant bule 3G at 1 hour sulfonation reaction time.
Embodiment 12
Repeat operating process and processing condition described in the embodiment 1, just in the step (c) of embodiment 1, during 50 ℃ of hydrolysis temperatures, hydrolysis time 12 hours finally obtains 8.1 parts hair reactive brilliant bule 3G.
Comparing embodiment
Repeat operating process and processing condition described in the embodiment 1, just change debrominate temperature in the step (e) of embodiment 1 into 15 ℃, pH value 12～13 finally obtains 9.2 parts hair reactive brilliant bule 3G; Test result is equivalent to 75% of product staining power among the embodiment 1.
The dyestuff Application Example
Embodiment 13
Dyestuff is pressed 1%o.w.f (relatively fabric heavy) consumption; bath raio 1: 20; be 1g/L at acetic acid concentration; A Baige B concentration is under the 1g/L condition; the wool fiber through precooking is lowered in room temperature dyes, and the speed with 1 ℃/min under continuing to stir is warming up to 95 ℃, insulation dyeing 60min; cool to 60 ℃ then, washing.
Dye sample again through fixation treatment, washing is dried.Present bright-coloured blueness at wool.Have excellent degree of fixation, lifting force and every colour fastness.
The performance test data of dyestuff sees Table 1, table 2, table 3, and the Integ value namely records the integrated value of each wavelength of K/S in the table 2 at spectrometer.
Table 1 mao is with reactive brilliant bule 3G and Lanasol Blue 3G dye uptake and degree of fixation contrast test result
| Sample | Lanasol Blue 3G | Hair reactive brilliant bule 3G |
| Dye uptake (%) | 98.40 | 99.17 |
| Degree of fixation (%) | 87.58 | 88.66 |
Table 2 mao influences the contrast test result with reactive brilliant bule 3G and Lanasol Blue 3G dye level to the color depth value
| Dye level (%) | 0.5 | 1.0 | 2.0 | 4.0 | 5.0 | 6.0 |
| Lanasol Blue 3G | 10.4778 | 20.2637 | 40.2845 | 58.4704 | 63.4747 | 76.8540 |
| Hair reactive brilliant bule 3G | 10.7520 | 20.7847 | 42.7143 | 58.7568 | 63.9636 | 79.4474 |
Table 3 is the colour fastness contrast test result on wool fabric mao with reactive brilliant bule 3G and Lanasol Blue 3G
Embodiment 2～12 prepared every application performance indexs of reactive brilliant bule 3G are same as the test result of embodiment 1.
Claims (9)
1. one kind prepares the method that hair is used reactive brilliant bule 3G, and it is characterized in that may further comprise the steps: 1) bromamine acid and para aminoacet anilide carry out condensation under catalyst action, obtain condensation product after the acidification; 2) condenses oleum sulfonation, alkaline hydrolysis deacetylate again; 3) hydrolysate and 2,3-, two bromo propionyl chloro condensations, debrominate makes the gorgeous blue 3G of dye activity again.
2. in accordance with the method for claim 1, it is characterized in that: in bromamine acid and the para aminoacet anilide step of condensation, described catalyzer is selected from copper sulfate and tin protochloride, and the add-on of two kinds of catalyzer is respectively 5～10% of bromamine acid in mole; The molar ratio of bromamine acid and para aminoacet anilide is 1: 1～2.5, and condensation temp is 40～100 ℃, pH value 8～12.
3. in accordance with the method for claim 2, it is characterized in that: the molar ratio of bromamine acid and para aminoacet anilide is 1: 1～1.3, and the described catalyzer of disposable adding, condensation temp are 60～90 ℃, pH value 9～11.
4. in accordance with the method for claim 2, it is characterized in that: to obtain the condition of condenses be pH value 0～3 to acidification after bromamine acid and the para aminoacet anilide condensation, 5～80 ℃ of filtration temperatures.
5. in accordance with the method for claim 1, it is characterized in that: when condenses carries out sulfonation and hydrolysis reaction, the SO that dissociates in the oleum
3Content is 3～25%, free SO in condenses and the oleum
3Mol ratio be 1: 1.5～3.0～60 ℃ of sulfonation reaction temperature, 40～100 ℃ of hydrolysising reacting temperatures.
6. in accordance with the method for claim 5, it is characterized in that: 25～40 ℃ of sulfonation reaction temperature, oleum concentration 7%～15%; 70～100 ℃ of hydrolysising reacting temperatures.
7. in accordance with the method for claim 1, it is characterized in that: the temperature of reaction of hydrolysate and 2,3-, two bromo propionyl chloro condensations is-5～25 ℃, pH=3～9; The reinforced mol ratio of hydrolysate and 2,3-, two bromo propionyl chloros is 1: 1～1.5.
8. in accordance with the method for claim 1, it is characterized in that: 20～60 ℃ of debromination temperature, pH value 8～11.
9. in accordance with the method for claim 1, it is characterized in that: with obtaining hair behind the debromination with the direct spraying drying of reactive brilliant bule 3G dye solution, obtain product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788993A (en) * | 2015-05-12 | 2015-07-22 | 上海安诺其集团股份有限公司 | Dark blue dye composition for hair and preparation method thereof |
| CN104846661A (en) * | 2015-05-12 | 2015-08-19 | 上海安诺其集团股份有限公司 | Application of wool dark blue dye combination to wool or wool fabric dyeing |
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| US2713059A (en) * | 1952-01-18 | 1955-07-12 | Sandoz Ag | Level-dyeing dyestuffs of the anthraquinone series |
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| CH489581A (en) * | 1966-10-14 | 1970-04-30 | Ciba Geigy | Process for the production of new anthraquinone dyes |
| JPS5069130A (en) * | 1973-10-23 | 1975-06-09 | ||
| US4077987A (en) * | 1975-02-27 | 1978-03-07 | Bayer Aktiengesellschaft | Water-soluble anthraquinone dyestuff |
| US4693727A (en) * | 1984-11-08 | 1987-09-15 | Ciba-Geigy Corporation | Process for dyeing synthetic polyamide materials with fibre-reactive anthraquinone dyes |
| CN101585974A (en) * | 2008-12-12 | 2009-11-25 | 天津市德凯化工有限公司 | Method for preparing wool reactive-dye brilliant blue |
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| US2713059A (en) * | 1952-01-18 | 1955-07-12 | Sandoz Ag | Level-dyeing dyestuffs of the anthraquinone series |
| US3501505A (en) * | 1965-11-11 | 1970-03-17 | Ciba Ltd | 1 - amino - 4(4'alpha,beta-dibromopropionylamino and alpha - bromoacrylamino)-anilino) - 2,2'-anthraquinonedisulfonic acids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788993A (en) * | 2015-05-12 | 2015-07-22 | 上海安诺其集团股份有限公司 | Dark blue dye composition for hair and preparation method thereof |
| CN104846661A (en) * | 2015-05-12 | 2015-08-19 | 上海安诺其集团股份有限公司 | Application of wool dark blue dye combination to wool or wool fabric dyeing |
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