CN102660130B - Method for producing reductive direct black BCN raw dye - Google Patents
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Abstract
A method for producing reductive direct black BCN raw dye comprises the following steps: a. brominating BO (bromine) in a non-organic solvent and a non-inorganic acid to obtain purple anthrone bromide; b. performing solid phase reaction, and performing condensation reaction on the purple anthrone bromide and 1-amino anthraquinone under the action of a catalyst and an acid binding agent to obtain a crude reductive direct black BCN dye; and c. acidifying the crude reductive direct black BCN dye and removing impurities to obtain the reductive direct black BCN raw dye. The method has the advantages as follows: firstly, in the BO brominating process, any organic solvent or any inorganic acid is not used, only an oxidant is added into water, and the bromination speed is high; secondly, the condensation reaction does not need any solvent and can be finished by heating in a solid phase container, so that the condensation reaction is very safe and environment-friendly; and thirdly, after the crude dye is acidified and copper is removed, the heavy metal content meets an ETAD requirement.
Description
Technical field
The invention belongs to technical field of dye, relate to the preparation method of anthraquinone type vat dyes, relate in particular to the production method of a kind of vat direct black BCN.
Background technology
Along with improving constantly of people's living standard, to the requirement of clothes, also, by former durable, change safety, environmental protection, comfortable, attractive in appearance into; Requirement to dyestuff is also more and more higher.Vat dyes is because be applicable to the dyeing of native cellulose fibre (silk, cotton), and safety, environmental protection, becomes the first-selection of fashion.
Black vat dye is the kind most important in vat dyes, consumption is maximum, wherein most important black kind---vat direct black RB (CASNo.1328-25-2)
Vat direct black RB is for the dyeing of cotton fibre, and level-dyeing property and avidity are all good, can directly dye to obtain black.Also be applicable to the stamp of cotton.Also for dye viscose fiber, silk and vinylon and cotton blend fabric and for polyester-cotton blend, wash glutinous fabric and dye black and dark-grey, Dry Sack is even.
Its preparation technology is: take vat golden orange G (C.I59700) as main raw material, first by its bromination, then, under sodium acetate and cupric oxide existence, contract and obtain product with 1-aminoanthraquinone and amino violanthrone.After filtration, be dried to obtain finished product.
This complex manufacturing, consumes highly, seriously polluted, and dye yield is low, meets the water drawback that easily reddens etc. and day by day manifests, and adds the increasingly stringent of environmental regulation, more and more can not meet the need of market and social demand.
In order to address this problem, the company of reaching has researched and developed the vat dyes of properties excellence---vat direct black BCN, to replace vat direct black RB.Vat direct black BCN is a new vat dyes, and it can not decomposite aromatic amine containing aromatic amine yet, and or not containing polychlorobiphenyl, heavy metal content does not reach ETAD standard, is the dyestuff of an environment-friendly type.B150reactive Black B 150 BCN has excellent dyefastness, and particularly to float fastness all good for its light fastness, crock fastness and chlorine.Also there is the wet and little feature of flatiron variable color of meeting.That other black vat dye is incomparable.Vat direct black BCN can be used in dip-dye, pad dyeing, the stamp of cotton fabric, is particularly suitable for pigment pad dyeing.During dip-dye, should use first method, during dyeing, add soda ash, can make the dye yield of dyestuff be greatly improved.Vat direct black BCN is a high density dyestuff, can dye aterrimus processed or light gray, also can use with other vat dyes blending.
The operational path of vat direct black BCN is: 1, Vat Dark Blue BO reacts with bromine and generates bromination violanthrone.2, bromination violanthrone and the condensation of 1-aminoanthraquinone obtain vat direct black BCN dyestuff crude product 3, crude product obtains the former dyestuff of vat direct black BCN through acidifying.
There are the following problems for former operational path: the composition problem of (1) bromination violanthrone: the technique that BO bromination is traditional is to carry out in the vitriol oil, chlorsulfonic acid or oil of mirbane.Because of oil of mirbane severe toxicity, there are carcinogenic and bad courage and uprightness, be eliminated gradually; The vitriol oil is met a large amount of heat releases of water, can boil and spatter, and contacts vigorous reaction can occur with inflammable substance (as benzene) with combustiblematerials (as sugar, Mierocrystalline cellulose etc.), even causes burning; Chlorsulfonic acid is combustion-supporting, tool severe corrosive, strong and stimulating, and reaction finishes to decompose with a large amount of sulfuric acid, and result can produce again a large amount of sulfuric acid and hydrochloric acid, quite unfavorable to environment protection.(2) problem of bromination violanthrone and the condensation of 1-aminoanthraquinone: traditional technology completes in oil of mirbane.This reaction is not only poisoned greatly, and energy consumption is high.(3) heavy metal content problem: traditional technology is without acidifying copper removal, only poach, copper content exceedes ETAD limit standard.
Summary of the invention
The technical problem solving: for above-mentioned technological deficiency, the invention provides a kind of method of producing the former dyestuff of vat direct black BCN, present method, need not any organic solvent or mineral acid in BO bromination process, only adds oxygenant in water, just can complete.And bromination reaction speed is fast.Secondly, condensation reaction, without any need for solvent, is heated and can be completed, very safe, environmental protection in solid phase device.The 3rd, the thick acidified copper removal of dyestuff, heavy metal content reaches ETAD requirement.
Technical scheme: produce the method for the former dyestuff of vat direct black BCN, step is in mass parts:
The preparation of a, bromination violanthrone: add 1 part of BO filter cake in 14 parts of water, after making beating evenly, add 0.3 part of sodium chlorate, 0.7 part of bromine, is warming up to 70～100 ℃, be incubated 2～6 hours, be warming up to 80 ℃, Distillation recovery bromine, has steamed, be down to room temperature, filtration, washing to neutral, obtain bromination violanthrone;
The preparation of b, crude product dyestuff: solid state reaction: add 15～20 parts of bromination violanthrones, 10～13 parts of 1-aminoanthraquinone, 1～3 part of copper catalyst, 3～10 parts of soda ash, be warming up to 120～130 ℃ of dehydrations, be warming up to again 210～260 ℃, be incubated 2～5 hours, be cooled to below 100 ℃, discharging, obtains crude product dyestuff after poach;
The preparation of c, the former dyestuff of vat direct black BCN: 1 part of crude product dyestuff, 1～3 part of strong acid is pulled an oar in 10 parts of water, is warming up to 70～100 ℃, is incubated 5 hours, filters, and obtains the former dyestuff of vat direct black BCN.
In step a, the optimum temperature of bromination reaction is 80～95 ℃.
In step b, the optimum temperature of solid state reaction is 230～250 ℃.
In step c, the strong acid used of acidifying removal of impurities is the sulfuric acid of hydrochloric acid or 98%wt, and most suitable reaction temperature is 80～90 ℃.Each step reaction equation is as follows:
Bromination:
Condensation
Beneficial effect:
1, bromination is in water, rather than carries out in oil of mirbane or chlorsulfonic acid, the vitriol oil, not only save material, and safety, environmental protection, energy-conservation, consumption reduction;
2, condensation adopts solid state reaction, need not any solvent, abandon the traditional technology of making solvent with severe toxicity, high boiling oil of mirbane, and reduced discharge poisonous, obnoxious flavour; Healthy favourable to site environment, operator; Save mass energy, there is good economic and social benefit;
3, acidifying removing heavy metals, improving product quality, improves dye shade and application performance, makes it to reach ETAD standard, for product exports America and Europe smoothly, has created favourable condition.
Accompanying drawing explanation
Fig. 1 is synthesis route figure of the present invention;
Fig. 2 is dyeing K/S curve, and X-coordinate is absorbing wavelength, the nm of unit, and ordinate zou is K/S value.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should declare, these embodiment are only not used in and limit the scope of the invention for invention is described.
Embodiment 1
At 250mL there-necked flask (dress thermometer, reflux exchanger, in condenser, pass into chilled brine, upper attached vapor pipe and device for absorbing tail gas, to get rid of the sour gas such as HBr of generation) in add water 210g, open and stir, add Vat Dark Blue BO 15g, pull an oar 2 hours, add sodium chlorate 4.5g, bromine 10.5g, be warming up to 70～100 ℃, at 70～100 ℃ of temperature, stir 5 hours.Distillation recovery bromine, is cooled to 50 ℃, and filter, wash to neutral, the dry bromination violanthrone that to obtain, yield counts 130% with violanthrone.Product after testing its bromine content is 25.89% (theory is 26.1%).It is ruddiness navy blue that product dyes cotton.
Embodiment 2
At 500mL there-necked flask (dress thermometer, reflux exchanger, in condenser, pass into chilled brine, upper attached vapor pipe and device for absorbing tail gas, to get rid of the sour gas such as HBr generating) in add water 350g, open and stir, add 25g BO filter cake making beating 2 hours, add sodium chlorate 7.5g, bromine 17.5g, is warming up to 70～100 ℃, at 70～100 ℃ of temperature, stirs 6 hours.Distillation recovery bromine, is cooled to 50 ℃.Filter, wash to neutral, the dry bromination violanthrone that to obtain, yield counts 132% with violanthrone.Product after testing its bromine content is 26.32% (theory is 26.1%).It is ruddiness navy blue that product dyes cotton.
Embodiment 3
Utilize solid state reaction, add the bromination violanthrone 15g obtaining in embodiment 1,1-aminoanthraquinone 13g, soda ash 8g, cupric oxide 1g, mix and blend half an hour, is warming up to 120～130 ℃, dewaters 1 hour, continues to be warming up to 230～260 ℃, is incubated 5 hours.Be cooled to below 60 ℃, discharging, obtains 38g dyestuff crude product.
The crude product obtaining is added in 600mL water, boil 1 hour, cooling, filters, and washing is to neutral, dry, obtains 28g dry product.
Embodiment 4
Utilize solid state reaction, add the bromination violanthrone 20g obtaining in embodiment 2,1-aminoanthraquinone 13g, soda ash 8g, cupric chloride 1.1g, mix and blend half an hour, is warming up to 120～130 ℃, dewaters 1 hour, continues to be warming up to 230～260 ℃, is incubated 6 hours.Be cooled to below 60 ℃, discharging, obtains 40g dyestuff crude product.
The crude product obtaining is added in 600mL water, boil 1 hour, cooling, filters, and washing is to neutral, dry, obtains 30g dry product.
Embodiment 5
Under stirring, by the dyestuff dry product 20g obtaining in embodiment 4, join in 200mL water and pull an oar, and the sulfuric acid that adds 25g 98%wt is warmed up to 90 ℃, be incubated 5 hours, cool to 50 ℃, filter, washing is to neutral.Dry, obtain the former dyestuff of 18g vat direct black BCN.
Embodiment 6 (application example)
In 300mL pottery dye vat, add the former dyestuff in 0.05g embodiment 5,2mL 5%wt pulls open powder solution, 1mL ethanol, add containing 200 parts of the reduced liquids of vat powder 0.85g, NaOH1.1g, be warming up to 60 ℃, reduce 15 minutes, add 5g cotton fabric, 60 ℃ of dyeing 45 minutes.By fabric washing, atmospheric oxidation, uses 0.5%wt soap lye soap boiling 15 minutes, cleans, and dries, and obtains black-dyeing product.
These black-dyeing product are compared with reduction vat direct black BCN standard substance, and intensity is 100.6% of standard substance, coloured light Δ a=0.002, Δ b=0.004, dyeing K/S curve consistent with standard substance (Fig. 2).Explanation is vat direct black BCN according to the dyestuff of embodiments of the invention system, and quality index conformance with standard product.
Claims (4)
1. the method for producing vat direct black BCN former dyestuff, is characterized in that step is, in mass parts:
The preparation of a, bromination violanthrone: add 1 part of Vat Dark Blue BO filter cake in 14 parts of water, after making beating evenly, add 0.3～0.5 part of sodium chlorate, 0.4～1.4 part of bromine, is warming up to 70～100 ℃, is incubated 2～6 hours, 80 ℃ of Distillation recovery bromines of temperature, steamed, be down to room temperature, filtration, washing to neutral, obtained bromination violanthrone;
The preparation of b, thick dyestuff: solid state reaction: add 15～20 parts of bromination violanthrones, 10～13 parts of 1-aminoanthraquinone, 1～3 part of copper catalyst, 3～10 parts of soda ash, be warming up to 120～130 ℃ of dehydrations
,be warming up to 210～260 ℃ again, be incubated 2～5 hours, be cooled to below 100 ℃, discharging, obtains crude product dyestuff after poach;
The preparation of c, the former dyestuff of vat direct black BCN: 1 part of crude product dyestuff, 1～3 part of strong acid is pulled an oar in 10 parts of water, is warming up to 70～95 ℃, is incubated 5 hours, filters, and obtains the former dyestuff of vat direct black BCN, and strong acid used is the sulfuric acid of hydrochloric acid or 98wt.%.
2. the method for production vat direct black BCN according to claim 1, is characterized in that in step a, the optimum temperature of bromination reaction is 80～95 ℃.
3. the method for production vat direct black BCN according to claim 1, is characterized in that in step b, the optimum temperature of solid state reaction is 230～240 ℃.
4. the method for production vat direct black BCN according to claim 1, is characterized in that in step b, solid state reaction catalyzer used is copper powder, cupric oxide or cupric chloride.
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| CN104448888A (en) * | 2014-11-29 | 2015-03-25 | 萧县凯奇化工科技有限公司 | Preparation method of vat olive green B |
| CN109608902B (en) * | 2019-01-08 | 2020-04-28 | 徐州工业职业技术学院 | Anthraquinone vat dye blue BCR and preparation method thereof |
| CN112266627A (en) * | 2020-09-16 | 2021-01-26 | 徐州工业职业技术学院 | Anthraquinone vat dye black BN and preparation method thereof |
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| GB325525A (en) * | 1928-08-21 | 1930-02-21 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of halogen substitution products of the dibenzanthrone and isodibenzanthrone series |
| GB340262A (en) * | 1929-06-21 | 1930-12-22 | Ig Farbenindustrie Ag | Process for the manufacture and production of dibenzanthrones and isodibenzanthronescontaining chlorine and bromine |
| GB419666A (en) * | 1933-05-10 | 1934-11-12 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of vat dyestuffs |
| CH404035A (en) * | 1960-10-14 | 1965-12-15 | Ciba Geigy | Process for the production of vat dyes of the dibenzanthrone series, which are free from acidic water-solubilizing groups |
| DE3140897A1 (en) * | 1981-10-15 | 1983-04-28 | Basf Ag, 6700 Ludwigshafen | METHOD FOR USING LIGHT OF THE WAVELENGTHS 470 TO 600 NM FOR THE PHOTOSYNTHESIS |
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