CN102174272A - Preparation method and product of sulphur black dye - Google Patents
Preparation method and product of sulphur black dye Download PDFInfo
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- CN102174272A CN102174272A CN2011100643445A CN201110064344A CN102174272A CN 102174272 A CN102174272 A CN 102174272A CN 2011100643445 A CN2011100643445 A CN 2011100643445A CN 201110064344 A CN201110064344 A CN 201110064344A CN 102174272 A CN102174272 A CN 102174272A
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Abstract
The invention discloses a preparation method of a sulphur black dye. The method comprises the following steps: adding a sulphur black intermediate filter cake in water, heating to 90-100 DEG C while stirring, and adding the mixture in a sodium sulfide or sodium sulfide solution; then pulping for 30-60 minutes, adding a dispersant, and stirring for 5-30 minutes; and finally drying to obtain the sulphur black dye. The invention also discloses the sulphur black dye prepared by the method. By adding the dispersant in the dye, the strike rate of sulphur black on the cotton fabric and the cotton blended fabric can be increased, on the one hand, the dosage of the sulphur black can be reduced in the dyeing process, on the other hand, the amount of pollutants in printing and dyeing wastewater can be reduced, the treatment difficulty and environmental pollution of the printing and dyeing wastewater can be lowered, and the economic and environmental benefits are quite obvious.
Description
Technical field
The invention belongs to fine chemistry industry thioxine dyes technical field, specifically relate to a kind of preparation method and product of black sulfide dye.
Background technology
Thioxine dyes is to be interacted and the dyestuff that generates by some organic aromatic compound and sulphur or sodium polysulphide.Thioxine dyes is water insoluble, need it be reduced into solubility leuco compound sodium salt with sodium sulphite during dyeing, this leuco compound sodium salt has good avidity to Mierocrystalline cellulose and protein fibre, recovers again to become insoluble dyestuff and anchors on the fiber through oxide treatment again after the dyeing.
The raw material of thioxine dyes and production process are all fairly simple, with low cost, therefore raw material is simple and easy to, and washing and light fastness are better,, the requirement of thioxine dyes is very big, wherein very big with black, blue two kinds of dyestuffs especially at consumption aspect the cotton products dyeing, be the very big kind of output in the dyestuffs industries, be the conventional dyes of China, not only domestic needs amount of sulphur black is big, and very big market is arranged abroad.
In the sulphur black production process, mainly obtain: the preparation of (1) sodium polysulphide by following a few step reactions; (2) 2,4-dinitrochlorobenzene or 2,2, 4-dinitrophenol add alkali reaction and generate 2, the 4-sodium dinitrophenol; (3) 2,4-sodium dinitrophenols and sodium polysulphide vulcanize; (4) mixture after the sulfuration at last through oxidation, filter, size mixing, drying obtains the finished product.Traditional black sulfide dye in use, the general employing adds entry and sodium sulphite with filter cake in the middle of obtaining sulphur black after oxidation, filtration, the washing, heat up, with filter cake furnishing slurry, obtain the black sulfide dye commodity by roller drying or spraying drying then, but ubiquity situations such as dye uptake is low, dyeing behavior is not good in the black sulfide dye dyeing course of these method preparations.
Summary of the invention
The invention provides a kind of preparation method of high-performance black sulfide dye, this method is by adding multiple auxiliary agent in preparation dyestuff process, increased the avidity of black sulfide dye to fiber, thereby increased the dye uptake of sulphur black on cotton fabric, improved its dyeing behavior, reduce the production cost of sulphur black and, have certain economic and environmental benefit the pollution of environment.
The present invention also provides the black sulfide dye that is obtained by method for preparing product, and when this product was used to dye, every fastness ability was all excellent; Under equal conditions, has higher dye uptake than traditional black sulfide dye.
A kind of preparation method of black sulfide dye comprises: filter cake in the middle of the sulphur black is added in the entry, be warming up to 90～100 ℃ under the agitation condition, add sodium sulphite or sodium sulfide solution, pulled an oar then 30～60 minutes, add dispersion agent, stirred 5～30 minutes, last drying obtains black sulfide dye.
Be chosen under 90～100 ℃ of conditions and react, helping the sulphur black filter cake on the one hand fully is uniformly dispersed at water, on the other hand, filter cake and sodium sulphite are reflected under 90～100 ℃ of conditions and can fully react in the middle of the sulphur black, guarantee the sulphur black filter cake is reduced into the sulphur black slurry fully.
The weight percent that described raw material adds is: the filter cake amount of giving money as a gift in the middle of the sulphur black: sodium sulphite: dispersion agent=100: 10～20: 1～30.Described dispersion agent is a dye field dispersion agent commonly used, experiment shows, when adopting in the formaldehyde condensation products (Dispersant MF), sodium methylene bis-naphthalene sulfonate (dispersion agent NNO), desugar condensation sodium lignosulfonate dispersion agent of methyl naphthalene sulfonic acid sodium one or more, the Color of the dye product that obtains is best.The cohesion between the dye molecule has been avoided in the adding of dispersion agent greatly, has reduced the surface tension between liquid-liquid or the solid-liquid, is convenient to dyestuff and spreads to fabric, thereby improved the dye uptake of dyestuff.The weight percent that described raw material adds is preferably: the filter cake amount of giving money as a gift in the middle of the sulphur black: sodium sulphite: dispersion agent=100: 14～18: 10～30; Experiment shows that the amount for preparing pollutent in the dyeing waste water that obtains behind the dyestuff when selecting this raw material ratio for use can reduce significantly.
Described drying step can be selected roller drying, also can select spraying drying, can determine according to actual needs.Roller drying or spray-dired drying conditions all can carry out according to normal condition.
Filter cake can for example, at first utilize sulphur and sodium sulphite to prepare sodium polysulphide by existing method preparation in the middle of the described sulphur black; And then utilize 2, and 4-dinitrochlorobenzene or 2,2, 4-dinitrophenol and sodium hydroxide hydrolysis generate 2, the 4-sodium dinitrophenol; With 2,4-sodium dinitrophenol and sodium polysulphide vulcanize, the filter cake product that the mixture that obtains at last obtains through oxidation, filtration.Solid content in the middle of the preferred sulphur black in the filter cake is 40～80% (weight percents).
A kind ofly prepare the black sulfide dye mixture by above-mentioned preparation method, this mixture can be directly used in the dyeing of various cotton fabrics and BLENDED FABRIC thereof, and the dye uptake during dyeing is higher, and the usage quantity of the dyestuff under the equal conditions is less, and can reach Color preferably; It is lower to use this dyestuff to obtain in the waste water from dyestuff content of black sulfide dye simultaneously, and aftertreatment is simple.
The preparation method of black sulfide dye of the present invention, step is simple, employing adds dispersion agent in preparation process, improved the dye uptake of sulphur black on cotton fabric and BLENDED FABRIC thereof, the consumption of sulphur black when reducing dyeing on the one hand, reduce the amount of pollutent in the dyeing waste water on the other hand, reduce the difficulty of treatment of dyeing wastewater and to the pollution of environment, economy and environmental benefit are fairly obvious.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but is not limited to this.
Wherein, filter cake can be prepared by following method in the middle of the sulphur black of using in embodiment 1～6 and the Comparative Examples 1:
(1) preparation sodium polysulphide: in the 500mL there-necked flask, add entry 200mL, be warming up to 70 ℃, drop into sodium sulphite (60%) 147g, be warming up to 90 ℃ then, slowly drop into sulphur 112g, 95 ℃～100 ℃ insulation reaction one hour, standby;
(2) obtain 2, the preparation of 4-dinitrobenzene sodium: in the 1000mL there-necked flask, add entry 300mL, be warming up to 70 ℃, add 2,4-dinitrochlorobenzene 160g at 75～98 ℃ of dropwise liquid 210g, finishes, at 98 ℃～100 ℃ insulation reaction 60min, obtain 2,4-dinitrobenzene sodium;
(3) preparation of filter cake in the middle of the sulphur black: the sodium polysulphide that above-mentioned steps (1) is prepared 100 ℃～105 ℃ be added dropwise to prepare in the step (2) 2, in the 4-dinitrobenzene sodium, finish boiling 60min; Change over to and carry out vulcanization reaction in the 1L autoclave, at 140～145 ℃, pressure reacts 6h under the pressure of 0.18～0.22MPa, row pressure then, cooling, material is transferred to the 2000mL beaker of putting into water at the bottom of the 300mL, blast air at 65～75 ℃ and carry out oxidation, oxidization time is 2h, filters then, washing obtains the middle filter cake of sulphur black.
Embodiment 1:
In the beaker of 500mL, add the middle filter cake 50g (25g gives money as a gift) of entry and sulphur black, be warming up to 90 ℃, add sodium sulphite (60%) 3.5g, stirred 30 minutes at 90～95 ℃, in slurry, add Dispersant MF 0.5g then, making beating 30min is to all being flow-like, and is spray-dried, obtains sulphur black and gives money as a gift and be 28.5g.
Embodiment 2:
In the beaker of 500ml, add the middle filter cake 50g (25g gives money as a gift) of entry and sulphur black, be warming up to 90 ℃, add sodium sulphite (60%) 4g, stirred 40 minutes at 90～95 ℃, in slurry, add Dispersant MF 2.5g then, stir 5min, roller drying, sulphur black is given money as a gift and is 29.73g.
Embodiment 3:
In the beaker of 500ml, add the middle filter cake 50g (25g gives money as a gift) of entry and sulphur black, be warming up to 90 ℃, add sodium sulphite (60%) 4.5g, stirred 45 minutes at 90～95 ℃, in slurry, add Dispersant MF 7.5g then, stir 10min, drying, sulphur black is given money as a gift and is 34.20g.
Embodiment 4:
In the beaker of 500ml, add the middle filter cake 50g (25g gives money as a gift) of entry and sulphur black, be warming up to 95 ℃, add sodium sulphite (60%) 4g, stirred 55 minutes at 95～98 ℃, in slurry, add dispersion agent NNO2.5g then, stir 20min, spraying drying, sulphur black is given money as a gift and is 29.77g.
Embodiment 5:
In the beaker of 500ml, add the middle filter cake 50g (25g gives money as a gift) of entry and sulphur black, be warming up to 95 ℃, add sodium sulphite (60%) 3g, stirred 60 minutes at 95～98 ℃, in slurry, add sodium lignosulfonate 5g then, stir 15min, spraying drying, sulphur black is given money as a gift and is 32.29g.
Embodiment 6:
In the beaker of 500ml, add the middle filter cake 50g (25g gives money as a gift) of entry and sulphur black, be warming up to 95 ℃, add sodium sulphite (60%) 3.5g, stirred 45 minutes at 95～98 ℃, in slurry, add dispersion agent M 5g then, stir 25min, spraying drying, sulphur black is given money as a gift and is 30.21g.
Comparative Examples 1:
In the beaker of 500ml, add filter cake 50g (25g gives money as a gift) in the middle of entry and the sulphur black, be warming up to 95 ℃, add sodium sulphite (60%) 4g, stirred 40 minutes at 95～98 ℃, spraying drying, sulphur black is given money as a gift and is 27.72g.
The performance test example
The black sulfide dye that the foregoing description and Comparative Examples are made carries out performance test, and testing method is as follows:
Respectively take by weighing black sulfide dye that 1.5 grams make by embodiment 1～6 and Comparative Examples 1 in the 400mL beaker, the sodium sulfide solution 22.5mL that adds 100g/L, after stirring evenly, add the 200mL distilled water that boils, be stirred to the dyestuff off-bottom after, dye liquor is reduced to room temperature, be transferred in the 1000mL volumetric flask, to scale, shake up standby with distilled water diluting
Pipette 51.4mL, 53.6mL, 61.7mL, 53.7mL, 58.2mL, 54.5mL respectively, 50mL (guarantees that the former dyestuff total amount of its sulphur black is the same) by the good dye solution of constant volume of embodiment 1～6 and Comparative Examples 1 preparation in the 300mL dye vat, add the Carbon Dioxide sodium solution of the 50g/L of the 100g/L anhydrous slufuric acid sodium solution of 10mL and 2mL respectively, adding distil water is to 200mL again.Be warming up to 30～40 ℃, put into the 5g cotton respectively and dye, spare no effort to stir when just going into to dye, be warming up to 90～95 ℃ in 30min, 45min dyes under this temperature.Dye and finish to take out, drop into the abundant rinsing of flowing water, strand is done, and ventilative 10 minutes, clean with clear water again, dry naturally or in 60 ℃ of dryings.
Observe cloth specimen coloured light and adopt GB/T 2376-1980 to measure its staining power, coloured light, measure its dye uptake according to the method for GBT-9337-2009; Survey the COD of its pin water then
Cr(chemical oxygen demand (COD)), COD
CrDetection method adopt the COD determination method: potassium dichromate process, measurement result sees Table 1.
Table 1
| Embodiment | Coloured light | Intensity (%) | Dye uptake (%) | Pin water COD cr(mg/L) |
| 1 | Gorgeous 0.3-red 0.1 | 103％ | 69.04 | 6485 |
| 2 | Gorgeous 0.3-red 0.1 | 118％ | 78.65 | 3253 |
| 3 | Gorgeous 0.2-red 0.3 | 115％ | 77.4 | 3516 |
| 4 | Gorgeous 0.2-red 0.1 | 120％ | 80.21 | 3015 |
| 5 | Gorgeous 0.2-red 0.1 | 116％ | 77.48 | 3305 |
| 6 | Gorgeous 0.2-red 0.1 | 121％ | 80.45 | 3055 |
| Comparative Examples 1 | Gorgeous 0.1-red 0.1 | 100％ | 67.3 | 6765 |
Adopt GB/T 3921-1997, GB/T 3920-1997 to measure its dyefastness, measurement result such as table 2 (annotate: the standards for dyeing degree of depth is 6% (owf)).
Table 2
From above embodiment and Comparative Examples more as can be seen, the present invention can improve the dye uptake of sulphur black at cotton fabric by add dispersion agent in the sulphur black filter cake, reduce the production cost and the product consumption of sulphur black, improved the competitive power of sulphur black on market, and dyeing waste water COD
CrReduce greatly, reduce the intractability of dyeing waste water and the pollution of environment; When the dyestuff that is prepared by embodiment 2～6 is used for actual dyeing especially, the COD of dyeing waste water
CrCOD than the dyeing waste water that directly uses untreated sulphur black (Comparative Examples 1 prepares) dyeing to obtain
CrSignificantly reduce; In addition, have every fastness ability of thioxine dyes provided by the invention all more excellent, particularly fastness to perspiration and fastness to rubbing obviously improve.
Claims (7)
1. the preparation method of a black sulfide dye comprises: filter cake in the middle of the sulphur black is added in the entry, be warming up to 90～100 ℃ under the agitation condition, add sodium sulphite or sodium sulfide solution, pulled an oar then 30～60 minutes, add dispersion agent, stirred 5～30 minutes, last drying obtains black sulfide dye.
2. the preparation method of black sulfide dye according to claim 1 is characterized in that, the weight percent that described raw material adds is: the filter cake amount of giving money as a gift in the middle of the sulphur black: sodium sulphite: dispersion agent=100: 10～20: 1～30.
3. the preparation method of black sulfide dye according to claim 2 is characterized in that, the weight percent that described raw material adds is: the filter cake amount of giving money as a gift in the middle of the sulphur black: sodium sulphite: dispersion agent=100: 14～18: 10～30.
4. the preparation method of black sulfide dye according to claim 1 is characterized in that, described dispersion agent comprises one or more in formaldehyde condensation products, sodium methylene bis-naphthalene sulfonate and the desugar condensation sodium lignosulfonate of methyl naphthalene sulfonic acid sodium.
5. the preparation method of black sulfide dye according to claim 1 is characterized in that, described dry roller drying or the spraying drying of adopting.
6. the preparation method of black sulfide dye according to claim 1 is characterized in that, the solid content in the middle of the described sulphur black in the filter cake is 40～80%.
7. the black sulfide dye for preparing according to the described preparation method of the arbitrary claim of claim 1～6.
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| CN2011100643445A CN102174272A (en) | 2011-03-17 | 2011-03-17 | Preparation method and product of sulphur black dye |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280548A (en) * | 2015-05-21 | 2017-01-04 | 大连市旅顺口区江西化工工业总公司 | A kind of water solublity sulfuration is red and preparation method thereof |
| CN106634043A (en) * | 2016-12-24 | 2017-05-10 | 叶宗瑞 | Environment-friendly disperse dye and preparation method thereof |
| WO2017075909A1 (en) * | 2015-11-02 | 2017-05-11 | 深圳市国华光电科技有限公司 | Pure black dye and preparation method therefor, and electrowetting displaying ink |
| CN109403069A (en) * | 2018-08-20 | 2019-03-01 | 绍兴华星丝织印染有限公司 | A kind of dyeing of TR looped fabric |
| CN113582849A (en) * | 2020-04-30 | 2021-11-02 | 浙江省常山长盛化工有限公司 | Method for producing sulfur black based on mixed low oil of physically purified 2, 4-dinitrochlorobenzene |
| CN111100475B (en) * | 2020-01-08 | 2022-02-18 | 山西临汾染化(集团)有限责任公司 | Preparation method of sulfur dye |
| CN115605640A (en) * | 2020-03-13 | 2023-01-13 | 恒德利公司（Us） | Method for dyeing textiles with lignin |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280548A (en) * | 2015-05-21 | 2017-01-04 | 大连市旅顺口区江西化工工业总公司 | A kind of water solublity sulfuration is red and preparation method thereof |
| WO2017075909A1 (en) * | 2015-11-02 | 2017-05-11 | 深圳市国华光电科技有限公司 | Pure black dye and preparation method therefor, and electrowetting displaying ink |
| CN106634043A (en) * | 2016-12-24 | 2017-05-10 | 叶宗瑞 | Environment-friendly disperse dye and preparation method thereof |
| CN109403069A (en) * | 2018-08-20 | 2019-03-01 | 绍兴华星丝织印染有限公司 | A kind of dyeing of TR looped fabric |
| CN111100475B (en) * | 2020-01-08 | 2022-02-18 | 山西临汾染化(集团)有限责任公司 | Preparation method of sulfur dye |
| CN115605640A (en) * | 2020-03-13 | 2023-01-13 | 恒德利公司（Us） | Method for dyeing textiles with lignin |
| CN115605640B (en) * | 2020-03-13 | 2023-12-05 | 恒德利公司 | Method for dyeing textiles with lignin |
| CN113582849A (en) * | 2020-04-30 | 2021-11-02 | 浙江省常山长盛化工有限公司 | Method for producing sulfur black based on mixed low oil of physically purified 2, 4-dinitrochlorobenzene |
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Application publication date: 20110907 |