CN111100475B - Preparation method of sulfur dye - Google Patents
Preparation method of sulfur dye Download PDFInfo
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- CN111100475B CN111100475B CN202010016043.4A CN202010016043A CN111100475B CN 111100475 B CN111100475 B CN 111100475B CN 202010016043 A CN202010016043 A CN 202010016043A CN 111100475 B CN111100475 B CN 111100475B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000988 sulfur dye Substances 0.000 title claims abstract description 12
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims abstract description 18
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000004537 pulping Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 13
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 8
- RUFSYNQNEMIPEI-UHFFFAOYSA-N 1,3-dinitrobenzene hydrochloride Chemical compound [O-][N+](C1=CC([N+]([O-])=O)=CC=C1)=O.Cl RUFSYNQNEMIPEI-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- PGYZAKRTYUHXRA-UHFFFAOYSA-N 2,10-dinitro-12h-[1,4]benzothiazino[3,2-b]phenothiazin-3-one Chemical compound S1C2=CC(=O)C([N+]([O-])=O)=CC2=NC2=C1C=C1SC3=CC=C([N+](=O)[O-])C=C3NC1=C2 PGYZAKRTYUHXRA-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000975 dye Substances 0.000 abstract description 25
- 238000004043 dyeing Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 229920000742 Cotton Polymers 0.000 abstract description 4
- 239000004744 fabric Substances 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000002835 absorbance Methods 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- RQBWMLFHMVFSBS-UHFFFAOYSA-N 2,4-dinitrophenol;sodium Chemical compound [Na].OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RQBWMLFHMVFSBS-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- -1 dinitro nitrate Chemical compound 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B49/00—Sulfur dyes
- C09B49/02—Sulfur dyes from nitro compounds of the benzene, naphthalene or anthracene series
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/30—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using sulfur dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/6025—Natural or regenerated cellulose using vat or sulfur dyes
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a sulfur dye, which comprises the steps of (1) preparing sodium polysulfide; (2) hydrolyzing; (3) and vulcanizing; (4) oxidizing; (5) pulping; (6) and (5) drying. The preparation process for producing the sulfur black dye by using dinitrate prepared from ortho-nitrochlorobenzene as a raw material and the prepared sulfur black product have a green light value of-0.01 to-0.26 and a yellow light value of-0.03 to-0.25. Compared with the similar yellow-green light sulfur black dye, the black degree of the sulfur black dye on cotton fabrics is greatly improved, and the yellow-green light sulfur black dye produced by the invention has better decolorizing effect after dyeing.
Description
Technical Field
The invention relates to the field of fine chemical sulfur dyes, in particular to a preparation method of a sulfur dye.
Background
The sulfur black is a black phosphorus flaky solid, and is mainly used for dyeing cotton textiles. The sulfur black is made up by boiling 2, 4-dinitrophenol and sodium polysulfide in aqueous solution, and its production process is: (1) reacting sodium sulfide and sulfur to produce sodium polysulfide; (2) reacting the 2, 4-dinitrobenzene chloride with sodium hydroxide to produce 2, 4-dinitrophenol sodium; (3) producing sulfur black dye by carrying out vulcanization and oxidation reaction on 2, 4-dinitrophenol sodium and sodium polysulfide; (4) and mixing the slurry with sodium sulfide and drying to obtain the finished product. Wherein, in the production process of 2, 4-dinitro chlorobenzene, the catalyst is mainly obtained by the following steps: (1) preparing mixed acid; (2) preparing chlorobenzene; (3) dripping chlorobenzene into the mixed acid to complete nitration reaction; (4) and standing, separating and washing the nitrated mixture to obtain the final product 2, 4-dinitrochlorobenzene.
At present, a greenish yellow light sulfur black dye produced by 2, 4-dinitrochlorobenzene produced by chlorobenzene traditionally has green light value CIEDa of-0.2 to-0.5 and yellow light value of-0.2 to-0.5, which is larger, and the problems of common blackness of cloth samples, poor decolorizing effect after dyeing and the like exist in the dyeing process.
Disclosure of Invention
On the basis of the traditional process, the invention adopts the o-nitrochlorobenzene as the raw material to produce the 2, 4-dinitrochlorobenzene, and uses the 2, 4-dinitrochlorobenzene to produce the yellow-green light sulfur black dye, thereby improving the yellow-green light value, greatly improving the blackness of the sulfur black dye on cotton fabrics, and having better decolorizing effect after dyeing.
The invention is realized by adopting the following technical scheme:
a preparation method of a sulfur dye comprises the following steps:
(1) preparation of sodium polysulfide
Adding 100 parts of water into a flask, heating to 75-85 ℃, adding 250 parts of 60% sodium sulfide (sodium sulfide), stirring until the sodium sulfide is completely dissolved, adding 275 parts of sulfur, and after the addition is finished, carrying out heat preservation reaction at 95-105 ℃ for 1.5 hours;
(2) hydrolysis of the mixture
100 parts of water and 160 parts of 2, 4-dinitrochlorobenzene are added into a flask, 160 parts of 30% caustic soda solution is dripped at 58-68 ℃, the reaction is controlled at 102-110 ℃, and the reaction is carried out for 1.5 hours under heat preservation for later use;
(3) and vulcanizing
Adding the prepared hydrolysis material and sodium polysulfide solution into a flask, and reacting for 1.5 hours at 100-110 ℃; transferring the material to a magnetic stirring pressure kettle, heating to 142-149 ℃, reacting for 8 hours, controlling the reaction pressure to be 0.15MPa, finishing the reaction, exhausting and decompressing, and recovering the exhausted gas;
(4) and oxidizing the mixture
Putting the vulcanized material into a beaker, adding 400-450 ml of water, heating to 59-69 ℃, introducing air below the liquid level by using an air blower, introducing the air for 3 hours, carrying out suction filtration on the oxidized material by using a vacuum pump, and washing with water;
(5) pulping
Putting the washed filter cake into a beaker, adding 450ml of water, heating to 65-70 ℃, adding 45 parts of sodium sulfide, and stirring for 1.5 hours;
(6) drying the mixture
And (3) putting the pulped materials into a tray, putting the tray into an oven, heating to 100-110 ℃, and preserving heat for 8 hours to obtain the sulfur dye.
Wherein, the preparation of the 2, 4-dinitrochlorobenzene is as follows: adding o-nitrochlorobenzene into a container, heating to 55 ℃, starting stirring, beginning to dropwise add metered mixed acid, dropwise adding for 1h, controlling the whole dropwise adding process to be 47 +/-2 ℃, and preserving heat for 15 minutes; after the heat preservation is finished, heating the mixture to 90-120 ℃ in 1 hour, and preserving the heat for 3 hours; after the reaction is finished, standing for 40min, and separating to obtain the product 2, 4-dinitrochlorobenzene. The 2, 4-dinitrochlorobenzene accounts for 30-100% of the raw material.
The color light value of the sulfur black dye prepared by the method is as follows: green light value CIEDa of-0.01 to-0.26 and yellow light value of-0.03 to-0.25. Compared with the similar yellow-green light sulfur black dye, the black degree of the sulfur black dye on cotton fabrics is greatly improved, and the yellow-green light sulfur black dye produced by the invention has better decolorizing effect after dyeing.
Drawings
FIG. 1 shows a process flow diagram for preparing 2, 4-dinitrochlorobenzene from ortho-nitrochlorobenzene.
FIG. 2 shows an absorbance spectrum of the sulfur black dye prepared in example 2.
FIG. 3 shows an absorbance spectrum of the sulfur black dye prepared in example 3.
Detailed Description
The following provides a detailed description of specific embodiments of the present invention.
Firstly, o-nitrochlorobenzene is used as a raw material to prepare 2, 4-dinitrochlorobenzene, the process flow is shown in figure 1, concentrated nitric acid and concentrated sulfuric acid are prepared into mixed acid (the ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 1), and the mixed acid reacts with the o-nitrochlorobenzene in a dropwise manner at 90-120 ℃ to generate acidic dinitro and nitration waste acid. The acidic dinitro nitrate is washed by water and alkali to generate dinitro (2, 4-dinitro benzene chloride). The 2, 4-dinitro chlorobenzene produced by o-nitrochlorobenzene accounts for 30-100% of the raw material, and the color light of the sulfur black product is adjusted by adjusting the proportion of dinitrate produced by o-nitrochlorobenzene in the raw material. The nitrified waste acid reacts with the paranitrate to generate paranitrate for reaction and pumped waste acid. The extracted waste acid is evaporated and concentrated to generate concentrated sulfuric acid which is recycled in the system. The specific example is examples A1-A3.
Example A1
100g of o-nitrochlorobenzene was added to a 1000ml Erlenmeyer flask, the temperature in the vessel was heated to about 55 ℃ and stirring was started, and 180g of the metered mixed acid was added dropwise. The whole dropping process is controlled at 47 +/-2 ℃. Dropwise adding for about 1h, and keeping the temperature for 15 minutes. After the heat preservation is finished, the temperature is raised to about 100 ℃ in 1 hour, and the heat preservation is carried out for 3 hours. After the reaction is finished, standing for 40min and separating. 198g of 2, 4-Dinitrochlorobenzene (DNCB) with purity of 90.23%, isomer of 9.77% and crystallization point of 44.8 ℃ is obtained.
Example A2
100g of o-nitrochlorobenzene was added to a 1000ml Erlenmeyer flask, the temperature in the vessel was heated to about 55 ℃ and stirring was started, and 180g of the metered mixed acid was added dropwise. The whole dropping process is controlled at 47 +/-2 ℃. Dropwise adding for about 1h, and keeping the temperature for 15 minutes. After the heat preservation is finished, the temperature is raised to about 100 ℃ in 2 hours, and the heat preservation is carried out for 3 hours. After the reaction is finished, standing for 40min and separating. The obtained product DNCB was 190g, purity 91.25%, isomer 8.75%, crystallization point 44.1 deg.C.
Example A3
100g of o-nitrochlorobenzene was added to a 1000ml Erlenmeyer flask, the temperature in the vessel was heated to about 55 ℃ and stirring was started, and 180g of the metered mixed acid was added dropwise. The whole dropping process is controlled at 47 +/-2 ℃. Dropwise adding for about 1h, and keeping the temperature for 15 minutes. After the heat preservation is finished, the temperature is raised to about 100 ℃ in 2.5 hours, and the heat preservation is carried out for 3 hours. After the reaction is finished, standing for 40min and separating. The obtained product DNCB was 195g, purity 90.23%, isomer 9.77%, crystallization point 44.9 ℃.
According to the method disclosed by the embodiment of the invention, the 2, 4-dinitrochlorobenzene is prepared by taking the o-nitrochlorobenzene as a raw material, and the 2, 4-dinitrochlorobenzene is used as the raw material to produce the yellowish green light sulfur black dye (the green light value is-0.01 to-0.26, and the yellow light value is-0.03 to-0.25). Meanwhile, the yellow-green light sulfur black product has better decolorizing effect after being dyed. The specific examples are as in examples 1 to 4.
Example 1
A preparation method of a sulfur dye comprises the following steps:
1. preparation of sodium polysulfide: 100g of water is added into a 500ml three-neck flask, the temperature is raised to 75 ℃, 250g of 60% sodium sulfide is added, the mixture is stirred until the mixture is completely dissolved, 275g of sulfur is added, and after the addition is finished, the mixture is subjected to heat preservation reaction at 95 ℃ for 1.5 hours.
2. Hydrolysis: 100g of 2, 4-dinitrobenzene chloride 160g and 30 percent caustic soda solution 160g are added into a 500ml three-neck flask, dropwise added at 58 ℃ and reacted at 102 ℃ for 1.5 hours for standby.
3. And (3) vulcanization: the hydrolysis material and the sodium polysulfide solution were charged into a 1000ml three-neck flask and reacted at 100 ℃ for 1.5 hours. Transferring the materials to a magnetic stirring pressure kettle, heating to 142 ℃, reacting for 8 hours, controlling the reaction pressure to be 0.15MPa, finishing the reaction, exhausting and decompressing, and recovering the exhausted gas.
4. And (3) oxidation: and (3) putting the vulcanized material into a 2500ml beaker, adding 400ml of water, heating to 59 ℃, introducing air below the liquid level by using an air blower for 3 hours, carrying out suction filtration on the oxidized material by using a vacuum pump, and washing with water.
5. Pulping: and (3) putting the filter cake washed by the water into a 1000ml beaker, adding 450ml of water, heating to 65 ℃, adding 45g of alkali sulfide, and stirring for 1.5 hours.
6. And (3) drying: and (3) putting the pulped materials into a tray, putting the tray into an oven, heating to 100 ℃, and preserving heat for 8 hours.
Example 2
A preparation method of a sulfur dye comprises the following steps:
1. preparation of sodium polysulfide: 100g of water is added into a 500ml three-neck flask, the temperature is raised to 80 ℃, 250g of 60% sodium sulfide is added, the mixture is stirred until the mixture is completely dissolved, 275g of sulfur is added, and after the addition is finished, the mixture is reacted for 1.5 hours at the temperature of 95 ℃.
2. Hydrolysis: 100g of 2, 4-dinitrobenzene chloride 160g and 30 percent caustic soda solution 160g are added into a 500ml three-neck flask, dropwise added at 63 ℃ and kept at 105 ℃ for 1.5 hours for reaction for standby.
3. And (3) vulcanization: the hydrolysis material and the sodium polysulfide solution were charged into a 1000ml three-neck flask and reacted at 105 ℃ for 1.5 hours. Transferring the materials to a magnetic stirring pressure kettle, heating to 147 ℃, reacting for 8 hours, controlling the reaction pressure to be 0.15MPa, finishing the reaction, exhausting and decompressing, and recovering the exhausted gas.
4. And (3) oxidation: and (3) putting the vulcanized material into a 2500ml beaker, adding 400ml of water, heating to 64 ℃, introducing air below the liquid level by using an air blower for 3 hours, carrying out suction filtration on the oxidized material by using a vacuum pump, and washing with water.
5. Pulping: and (3) putting the filter cake washed by the water into a 1000ml beaker, adding 450ml of water, heating to 70 ℃, adding 45g of alkali sulfide, and stirring for 1.5 hours.
6. And (3) drying: and (3) putting the pulped materials into a tray, putting the tray into an oven, heating to 105 ℃, and preserving heat for 8 hours.
The blackness obtained after dyeing with the dye can be seen from the absorbance of the dye, the absorbance of the maximum absorption wavelength of the general sulfur black dye is about 0.74, the maximum absorption wavelength of the sulfur black dye prepared in this example is 0.8+, and the absorbance map is shown in fig. 2.
Example 3
A preparation method of a sulfur dye comprises the following steps:
1. preparation of sodium polysulfide: 100g of water is added into a 500ml three-neck flask, the temperature is raised to 85 ℃, 250g of 60% sodium sulfide is added, the mixture is stirred until the mixture is completely dissolved, 275g of sulfur is added, and after the addition is finished, the mixture is reacted for 1.5 hours at 105 ℃.
2. Hydrolysis: 100g of 2, 4-dinitrobenzene chloride 160g and 30 percent caustic soda solution 160g are added into a 500ml three-neck flask, dropwise added at 68 ℃ and reacted for 1.5 hours at 110 ℃ for standby.
3. And (3) vulcanization: the hydrolysis material and the sodium polysulfide solution were charged into a 1000ml three-neck flask and reacted at 110 ℃ for 1.5 hours. Transferring the materials to a magnetic stirring pressure kettle, heating to 149 ℃, reacting for 8 hours, controlling the reaction pressure to be 0.15MPa, finishing the reaction, exhausting and decompressing, and recovering the exhausted gas.
4. And (3) oxidation: and (3) putting the vulcanized material into a 2500ml beaker, adding 400ml of water, heating to 69 ℃, introducing air below the liquid level by using an air blower, introducing the air for 3 hours, carrying out suction filtration on the oxidized material by using a vacuum pump, and washing with water.
5. Pulping: and (3) putting the filter cake washed by the water into a 1000ml beaker, adding 450ml of water, heating to 69 ℃, adding 45g of alkali sulfide, and stirring for 1.5 hours.
6. And (3) drying: and (3) putting the pulped materials into a tray, putting the tray into an oven, heating to 100 ℃, and preserving heat for 8 hours.
The blackness obtained after dyeing with the dye can be seen from the absorbance of the dye, the absorbance of the maximum absorption wavelength of the general sulfur black dye is about 0.74, the maximum absorption wavelength of the sulfur black dye prepared in this example is 0.8+, and the absorbance map is shown in fig. 3.
Example 4
A preparation method of a sulfur dye comprises the following steps:
1. preparation of sodium polysulfide: 100g of water is added into a 500ml three-neck flask, the temperature is raised to 85 ℃, 250g of 60% sodium sulfide is added, the mixture is stirred until the mixture is completely dissolved, 275g of sulfur is added, and after the addition is finished, the mixture is reacted for 1.5 hours at 105 ℃.
2. Hydrolysis: 100g of 2, 4-dinitrobenzene chloride 160g and 30 percent caustic soda solution 160g are added into a 500ml three-neck flask, dropwise added at 68 ℃ and reacted for 1.5 hours at 110 ℃ for standby.
3. And (3) vulcanization: the hydrolysis material and the sodium polysulfide solution were charged into a 1000ml three-neck flask and reacted at 110 ℃ for 1.5 hours. Transferring the materials to a magnetic stirring pressure kettle, heating to 149 ℃, reacting for 8 hours, controlling the reaction pressure to be 0.15MPa, finishing the reaction, exhausting and decompressing, and recovering the exhausted gas.
4. And (3) oxidation: and (3) putting the vulcanized material into a 2500ml beaker, adding 400ml of water, heating to 69 ℃, introducing air below the liquid level by using an air blower, introducing the air for 3 hours, carrying out suction filtration on the oxidized material by using a vacuum pump, and washing with water.
5. Pulping: and (3) putting the filter cake washed by the water into a 1000ml beaker, adding 450ml of water, heating to 69 ℃, adding 45g of alkali sulfide, and stirring for 1.5 hours.
6. And (3) drying: and (3) putting the pulped materials into a tray, putting the tray into an oven, heating to 110 ℃, and preserving heat for 8 hours.
TABLE 1 product color test report
As can be seen from Table 1, the sulfur black dye prepared in this example is superior to the common sulfur black dye on the market.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the detailed description is made with reference to the embodiments of the present invention, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which shall all fall within the protection scope of the claims of the present invention.
Claims (1)
1. A preparation method of sulfur dye is characterized in that: the method comprises the following steps:
(1) preparation of sodium polysulfide: adding 100g of water into a 500ml three-neck flask, heating to 85 ℃, adding 250g of 60% sodium sulfide, stirring until the sodium sulfide is completely dissolved, adding 275g of sulfur, and after the addition is finished, keeping the temperature at 105 ℃ for reaction for 1.5 hours;
(2) and (3) hydrolysis: 100g of 2, 4-dinitrobenzene chloride 160g and 30 percent caustic soda solution 160g are added into a 500ml three-neck flask, dropwise added at 68 ℃ and reacted for 1.5 hours at 110 ℃ for standby;
the preparation method of the 2, 4-dinitrochlorobenzene comprises the following steps: adding 100g of o-nitrochlorobenzene into a 1000ml triangular flask, heating to 55 ℃ of the temperature in the observation pot, starting stirring, and dropwise adding 180g of metered mixed acid; the whole dripping process is controlled to be 47 +/-2 ℃; dropwise adding for 1h, and keeping the temperature for 15 minutes; after the heat preservation is finished, heating the mixture to 100 ℃ in 2 hours, and preserving the heat for 3 hours; standing for 40min and separating after the reaction is finished; 190g of DNCB product obtained with the purity of 91.25 percent, 8.75 percent of isomer and the crystallization point of 44.1 ℃;
(3) and vulcanizing: adding the prepared hydrolysis material and sodium polysulfide solution into a 1000ml three-neck flask, and reacting for 1.5 hours at 110 ℃; transferring the materials to a magnetic stirring pressure kettle, heating to 149 ℃, reacting for 8 hours, controlling the reaction pressure to be 0.15MPa, finishing the reaction, exhausting and decompressing, and recovering the exhausted gas;
(4) and oxidizing: putting the vulcanized material into a 2500ml beaker, adding 400ml of water, heating to 69 ℃, introducing air below the liquid level by using an air blower, introducing the air for 3 hours, carrying out suction filtration on the oxidized material by using a vacuum pump, and washing with water;
(5) pulping: putting the washed filter cake into a 1000ml beaker, adding 450ml of water, heating to 69 ℃, adding 45g of sodium sulfide, and stirring for 1.5 hours;
(6) and (3) drying: and (3) putting the pulped materials into a tray, putting the tray into an oven, heating to 100 ℃, and preserving heat for 8 hours.
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| EP0741168A1 (en) * | 1995-05-03 | 1996-11-06 | Clariant Finance (BVI) Limited | Sulphur dyes |
| CN1513830A (en) * | 2003-07-29 | 2004-07-21 | 徐德军 | Preparation method of 2,4-dinitochloro benzene |
| CN1786079A (en) * | 2004-12-27 | 2006-06-14 | 阮加根 | Preparation process of sulfur black dye and product thereof |
| CN102174272A (en) * | 2011-03-17 | 2011-09-07 | 浙江长征化工有限公司 | Preparation method and product of sulphur black dye |
| CN102516796A (en) * | 2011-11-21 | 2012-06-27 | 苏州贵族公子服饰有限公司 | Preparation method for vulcanized reactive dye |
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|---|---|---|---|---|
| EP0741168A1 (en) * | 1995-05-03 | 1996-11-06 | Clariant Finance (BVI) Limited | Sulphur dyes |
| CN1513830A (en) * | 2003-07-29 | 2004-07-21 | 徐德军 | Preparation method of 2,4-dinitochloro benzene |
| CN1786079A (en) * | 2004-12-27 | 2006-06-14 | 阮加根 | Preparation process of sulfur black dye and product thereof |
| CN102174272A (en) * | 2011-03-17 | 2011-09-07 | 浙江长征化工有限公司 | Preparation method and product of sulphur black dye |
| CN102516796A (en) * | 2011-11-21 | 2012-06-27 | 苏州贵族公子服饰有限公司 | Preparation method for vulcanized reactive dye |
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