CN116694100A - Green-light black dye and preparation method and application thereof - Google Patents
Green-light black dye and preparation method and application thereof Download PDFInfo
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- CN116694100A CN116694100A CN202310640802.8A CN202310640802A CN116694100A CN 116694100 A CN116694100 A CN 116694100A CN 202310640802 A CN202310640802 A CN 202310640802A CN 116694100 A CN116694100 A CN 116694100A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000005859 coupling reaction Methods 0.000 claims abstract description 40
- 230000008878 coupling Effects 0.000 claims abstract description 18
- 238000010168 coupling process Methods 0.000 claims abstract description 17
- 238000004043 dyeing Methods 0.000 claims abstract description 14
- 238000010668 complexation reaction Methods 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 9
- 238000007639 printing Methods 0.000 claims abstract description 9
- DOPJTDJKZNWLRB-UHFFFAOYSA-N 2-Amino-5-nitrophenol Chemical compound NC1=CC=C([N+]([O-])=O)C=C1O DOPJTDJKZNWLRB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 115
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 61
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 36
- 239000000975 dye Substances 0.000 claims description 34
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 229950011260 betanaphthol Drugs 0.000 claims description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 16
- 239000004744 fabric Substances 0.000 claims description 15
- 230000000536 complexating effect Effects 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- ZRRGOUHITGRLBA-UHFFFAOYSA-N stattic Chemical compound [O-][N+](=O)C1=CC=C2C=CS(=O)(=O)C2=C1 ZRRGOUHITGRLBA-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YGNDWDUEMICDLW-UHFFFAOYSA-N 7-anilino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C=1C=C2C(O)=CC(S(O)(=O)=O)=CC2=CC=1NC1=CC=CC=C1 YGNDWDUEMICDLW-UHFFFAOYSA-N 0.000 claims description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 8
- 229920005610 lignin Polymers 0.000 claims description 8
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- 239000004677 Nylon Substances 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 229920001778 nylon Polymers 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 229960004889 salicylic acid Drugs 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 239000000980 acid dye Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000010985 leather Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 210000002268 wool Anatomy 0.000 claims description 4
- 229920006052 Chinlon® Polymers 0.000 claims description 2
- 238000012952 Resampling Methods 0.000 claims description 2
- 239000007853 buffer solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 5
- 230000001105 regulatory effect Effects 0.000 claims 2
- 238000002791 soaking Methods 0.000 claims 2
- 239000000376 reactant Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000007858 starting material Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000005254 chromizing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006149 azo coupling reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 150000001989 diazonium salts Chemical class 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VLZVIIYRNMWPSN-UHFFFAOYSA-N 2-Amino-4-nitrophenol Chemical compound NC1=CC([N+]([O-])=O)=CC=C1O VLZVIIYRNMWPSN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/01—Complex metal compounds of azo dyes characterised by the method of metallisation
-
- 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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
- C09B45/26—Disazo or polyazo compounds containing chromium
-
- 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
- D06P1/39—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 acid 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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/06—Material containing basic nitrogen containing amide groups using acid 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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
- D06P3/16—Wool using acid dyes
Abstract
The invention relates to the field of printing and dyeing, in particular to a green-light black dye and a preparation method thereof, wherein 2-amino-5-nitrophenol is taken as a starting material, a dispersing agent is added in two diazotization reactions and two coupling reactions, the obtained coupling compound can be directly subjected to complexation reaction without post treatment, and the obtained complex is dried to obtain a product; the green black dye has excellent chromatic light and is an environment-friendly dye.
Description
Technical Field
The invention relates to the field of printing and dyeing, in particular to a green-light black dye and a preparation method and application thereof.
Background
Compared with the common acid dye, the green black dye has more important dyeing uniformity and reproducibility than the common acid dye, and the industrial wastewater generated in the dye synthesis and printing and dyeing processes contains toxic substances, so that the production environment of factories is influenced, and the ecological environment is also influenced.
The acid black ACE is a green black dye, the structure of the acid black ACE belongs to an asymmetric metal complex dye, the acid black ACE has excellent fastness and wide application, and can be used for dyeing and printing fabrics such as wool, silk, chinlon and the like, and also can be used for leather, paper and the like. The synthesis process of the dye is longer, and comprises multiple diazotization, coupling and complexation reaction processes, so that the material proportion, end point control and the like are difficult to master, a plurality of post-treatment steps such as salting out, filtering and the like are required, and a large amount of industrial refined salt is added to precipitate the original dye, and then filtering is performed, so that a large amount of filtrate and washing liquid are generated, the salt content in waste water formed by the filtrate and the washing liquid is high, the COD content is also high, the waste water reaches the emission standard, the production cost of enterprises is obviously increased, and therefore, how to reduce the generation of the waste water becomes the key point of researchers.
Through searching the green-light black dye preparation method, the preparation method which is widely applied at present still comprises the steps of preparing a product through diazotization reaction and coupling reaction, removing impurities through filtration to improve the purity of the product, and then carrying out spray drying on the product to obtain the compound raw powder, so that the production of waste and waste water is reduced. However, in the process of repeated diazotization and coupling reaction, the coupling reaction condition is relatively harsh, the reaction process is relatively complex, and the compound is purified after each coupling reaction, which not only affects the yield of the final product, but also is one of the main reasons for industrial wastewater generation in dye preparation, and the generation of waste residues and wastewater is reduced only by spray drying the obtained product in the last step, so that the effect is very poor.
In summary, the development of an environment-friendly green-light black dye with stable color light and a preparation method thereof is needed in the market at present, and the production of waste water is reduced and the production cost is saved on the premise of not reducing the quality of green-light black products.
Disclosure of Invention
The invention aims to provide a green black dye;
another object of the present invention is to provide a method for preparing a green black dye and application thereof.
The technical scheme adopted for realizing the purpose of the invention is as follows:
1. solution configuration
Configuration of a.N-phenyl-J acid solution: dissolving N-phenyl-J acid in sodium hydroxide solution, controlling ph=8-10;
b, preparation of 2-amino-5-nitrophenol solution: uniformly stirring 2-amino-5-nitrophenol in a hydrochloric acid solution, and controlling the pH value to be 1-2;
c. preparation of nitrous acid solution: adding water into sodium nitrite to dissolve the sodium nitrite to prepare nitrous acid solution;
e. preparation of chromizing agent solution: adding water and formic acid into a reaction bottle to prepare a solution with the concentration of 50%, adding chromium oxide and NaOH solution under stirring, heating to 50 ℃, keeping the temperature, continuously stirring to dissolve the solution completely, and adding salicylic acid and stirring for 30 minutes;
configuration of g.6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid solution: adding 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid into water for dissolution, stirring for 30 minutes, slowly adding liquid alkali, and adjusting pH=3.5-4;
h, preparation of 2-naphthol solution: adding 2-naphthol into sodium hydroxide solution, heating to 50-60 ℃ and stirring uniformly to obtain 2-naphthol solution;
2. a preparation method of green-light black dye comprises the following specific reaction formula:
step one, diazotization reaction 1: preparation of solution b
Diazotization reaction 2: preparation of g solution
Step two, coupling reaction
Coupling reaction 1:
coupling reaction 2:
step three, complexation reaction
Complexing reaction 1:
complexing reaction 2:
the reaction conditions are as follows:
coupling reaction 1: c is added into b, the temperature is controlled to be 8-12 ℃, the pH is controlled to be less than 1, and the reaction is carried out for one hour; adding the reaction solution into the a, adding a dispersing agent, controlling the pH value to be 9.5-10.5, and reacting for two hours to obtain azo solution d;
the dispersing agent is one of lignin and NNO, and is used for inhibiting diazonium salt from decomposing in a coupling reaction, so that the reaction efficiency is improved, and the generation of wastewater is reduced;
complexing reaction 1: adding the coupling solution d and the chromizing agent solution e into a pressure reaction bottle, mixing, and adjusting the pH value to be 1-2 by hydrochloric acid; adding a small amount of 98% sulfuric acid, sealing the reaction bottle, heating to 140 ℃, controlling the pressure to 300-400 kPa, reacting for 4 hours under heat preservation, and cooling to room temperature for standby to obtain a complex solution f;
coupling reaction 2: adding h into g, controlling the temperature at 35-50 ℃, adding a dispersing agent, controlling the pH value to be 10-10.5, and reacting for two hours to obtain coupling liquid i;
the dispersing agent is one of lignin and NNO, and is used for inhibiting diazonium salt from decomposing in a coupling reaction, so that the reaction efficiency is improved, and the generation of wastewater is reduced;
complexing reaction 2: adding i into f, heating to 90 ℃, adding sodium hydroxide to pH=7.0-7.5, reacting for 1 hour, sampling for lamellar analysis, properly adjusting the micro excess of the complex f, continuously stirring for 3 hours, adding sodium hydroxide for adjusting the pH to 8.0, reacting for 30 minutes, resampling for lamellar analysis, reacting for the end point of the reaction, wherein the coupling compound i is required to completely react, and the micro excess of the complex f is obtained after the reaction is finished, so that the complex j is obtained;
after the end point is qualified, adding hydrochloric acid to adjust the pH to be 7.5, and evaporating to dryness to obtain a green black acid dye product; the green-black acid dye product can be obtained in a production workshop by utilizing a spray drying mode.
Compared with the prior art, the invention has the beneficial effects that:
1. the green-black dye prepared by the method has the advantages of bright coloring, good color saturation, good color uniformity of a product obtained by printing and dyeing, and excellent color fixation property.
2. The production process is environment-friendly, no wastewater is generated, the dispersing agent is added in the coupling reaction process to inhibit the decomposition of diazonium salt, and the filtering is not required to be repeated after the coupling reaction is finished, so that the reaction can directly take part in the next reaction, and the wastewater generation can be effectively reduced.
Drawings
FIG. 1 is a green black dye cloth dyeing test report according to an embodiment of the present invention;
FIG. 2 is a flow chart of the preparation method of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Example 1
(1) Diazo-coupling reaction 1
Uniformly stirring 18.7g of 2-amino-5-nitrophenol in a hydrochloric acid solution, and controlling the pH value to be 1-2; adding 9g of sodium nitrite and 30g of water to prepare nitrous acid solution, adding hydrochloric acid dropwise to control pH to be less than 1, and reacting for 1 hour; 15.56g of N-phenyl-J acid is dissolved in sodium hydroxide solution to be completely dissolved, added into the reaction solution, 0.5g of lignin is added, the pH value is controlled to be 9-9.5, the reaction is carried out for two hours at 20 ℃, and the coupling solution 1 is prepared for standby.
(2) Preparation of chromizing agent solution
20mL of water is added into a reaction bottle, 18.24g of chromium oxide, 4.8g of sodium hydroxide and 7.48g of formic acid are added under stirring, the temperature is raised to 50 ℃, the mixture is kept warm and stirred to dissolve all, 1.6g of salicylic acid is added, and the mixture is stirred for 30 minutes to prepare chromium liquid for standby.
(3) Complexation reaction 1
Adding the coupling solution 1 and the chromium solution into a pressure reaction bottle, heating to 50 ℃, and adjusting the pH to be 1 by using about 10.2g of 31% hydrochloric acid; then adding 1.28g of 98% sulfuric acid, sealing the reaction bottle, heating to 140 ℃, keeping the pressure at 300-400 kPa, and reacting for 4 hours to obtain the complex solution 1 for standby.
(4) Diazo-coupling reaction 2
Preparation of 42.43g 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid solution: dissolving 6-nitro in water, stirring for 30 min, slowly adding liquid alkali, adjusting pH=3.5-4.0, and stirring for 2 h;
preparation of 2-naphthol solution: adding 15.6g of 2-naphthol into alkaline solution, heating to 50-60 ℃ and stirring for dissolution; adding 0.5g lignin into the reaction solution, controlling pH=10-10.5, and reacting for two hours at 35-45 ℃.
Adding the prepared 2-naphthol solution into a 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid solution, controlling the temperature at 35-50 ℃, adding lignin, controlling the pH value to be 10-10.5, and reacting for two hours to obtain a coupling liquid 2.
(5) Complexation reaction 2
Adding the coupling solution 2 into the complexing solution 1, heating to 90 ℃, adding about 3.95g of sodium hydroxide, adjusting to pH=7.0-7.5, reacting for 1 hour, sampling for lamellar analysis, requiring small excess of the complexing solution 1, if the result is not excessive, carrying out proper adjustment, continuing stirring for 3 hours, adding sodium hydroxide for adjusting to pH=8.0, and reacting for 30 minutes.
(6) Drying
Adding hydrochloric acid to adjust the pH value to 7.0-7.5, directly evaporating to dryness, and drying to obtain 50.1g of dry material.
Example 2
(1) Diazo-coupling reaction 1
Uniformly stirring 18.7g of 2-amino-5-nitrophenol in a hydrochloric acid solution, controlling the pH value to be 1-2, adding water into 9g of sodium nitrite to dissolve to prepare a nitrous acid solution, adding hydrochloric acid to control the pH value to be less than 1, and reacting for 1 hour; 15.56g of N-phenyl-J acid is dissolved in sodium hydroxide solution, after the N-phenyl-J acid is completely dissolved, a reaction solution is added, 0.5g of NNO is added, the pH is controlled to be 10-10.5, the reaction is carried out for two hours at 20 ℃, and the coupling solution 1 is prepared for standby.
(2) Preparation of chromizing agent solution
To the reaction flask, 20mL of water was added, 18.24g of chromium oxide, 4.8g of sodium hydroxide and 7.48g of formic acid were added under stirring, the temperature was raised to 50℃and the mixture was stirred at a constant temperature to dissolve all of the components. 1.6g of salicylic acid is added and stirred for 30 minutes for later use.
(3) Complexation reaction 1
Adding the coupling solution 1 and the chromium solution into a pressure reaction bottle, heating to 50 ℃, and adjusting the pH to be 2 by using about 10.2g of 31% hydrochloric acid; then adding 1.28g of 98% sulfuric acid, sealing the reaction bottle, heating to 140 ℃, keeping the pressure at 300-400 kPa, and reacting for 4 hours to obtain the complex solution 1 for standby.
(4) Diazo-coupling reaction 2
Preparation of 42.43g 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid solution: dissolving 6-nitro in water, stirring for 30 min, slowly adding liquid alkali, adjusting pH=3.5-4.0, and stirring for 2 h;
preparation of 2-naphthol solution: 15.6g of 2-naphthol is added into alkaline solution, heated to 50-60 ℃ and stirred for dissolution, added into reaction solution, 0.5g of NNO is added, pH=10-10.5 is controlled, and reaction is carried out for two hours at 50 ℃.
Adding the prepared 2-naphthol solution into a 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid solution, controlling the temperature at 35-50 ℃, adding NNO, controlling the pH=10-10.5, and reacting for two hours to obtain a coupling solution 2.
(5) Complexation reaction 2
Adding the solution of the coupling solution 2 into the complexing solution 1, heating to 90 ℃, adding 3.95g of sodium hydroxide to pH=7.0-7.5, reacting for 1 hour, sampling for lamellar analysis, requiring small excess of the complexing solution 1, if the result is not excessive, properly adjusting, stirring, reacting for 3 hours, adding the sodium hydroxide to pH=8.0, and reacting for 30 minutes for later use.
(6) Drying
Adding hydrochloric acid to adjust the pH value to 7.0-7.5, directly evaporating to dryness, and drying to obtain 49.3g of dry material.
Example 3
(1) Diazo-coupling reaction 1
56.1g of 2-amino-5-nitrophenol is stirred uniformly in a hydrochloric acid solution, the pH=1-2 is controlled, 27g of sodium nitrite is dissolved in water to prepare a nitrous acid solution, the nitrous acid solution is added into the solution, the pH is controlled to be less than 1 by adding hydrochloric acid, and the reaction is carried out for 1 hour. 46.68g of N-phenyl-J acid is dissolved in sodium hydroxide solution to be completely dissolved, a reaction solution is added, 0.5g of lignin is added, the pH value is controlled to be 9-9.5, the reaction is carried out for two hours at 20 ℃, and the coupling solution 1 is prepared for standby.
(2) Preparation of chromizing agent solution
To the reaction flask, 60mL of water was added, and 54.72g of chromium oxide, 14.4g of sodium hydroxide and 22.44g of formic acid were added under stirring, and the temperature was raised to 50℃and the mixture was stirred under heat to dissolve all of the components. 4.8g of salicylic acid is added and stirred for 30 minutes for later use.
(3) Complexation reaction 1
The coupling solution 1 and the chromium solution were added to a pressure reaction flask, heated to 50 ℃, and ph=2 was adjusted with about 30.6g (31%) of hydrochloric acid; then adding 3.84g of 98% sulfuric acid, sealing the reaction bottle, heating to 140 ℃, keeping the pressure at 300-400 kPa, and reacting for 4 hours under the condition of heat preservation to obtain the complex solution 1 for standby.
(4) Diazo-coupling reaction 2
Preparation of 127.29g of 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid solution: dissolving 6-nitro in water, stirring for 30 min, slowly adding liquid alkali, adjusting pH=3.5-4.0, and stirring for 2 h;
preparation of 2-naphthol solution: 46.8g of 2-naphthol is added into alkaline solution, heated to 50-60 ℃ and stirred for dissolution, added into reaction solution, 0.5g of NNO is added, pH=10-10.5 is controlled, and the reaction is carried out for two hours at 45 ℃.
Adding the prepared 2-naphthol solution into a 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid solution, controlling the temperature at 35-50 ℃, adding any dispersing agent, controlling the pH value to be 10-10.5, and reacting for two hours to obtain a coupling liquid 2.
(5) Complexation reaction 2
Adding the coupling solution 2 solution into the complexing solution 1, heating to 90 ℃, adding 11.85g of sodium hydroxide to pH=7.0-7.5, reacting for 1 hour, sampling for lamellar analysis, requiring 1-bit excess chromizing, if the result is not excessive, properly adjusting, stirring, reacting for 3 hours, adding sodium hydroxide to pH=8.0, and reacting for 30 minutes.
(6) Drying
Adding hydrochloric acid to adjust to 7.0-7.5, and directly evaporating to dryness. 148.7g of dry material is obtained after drying.
Comparative example 1: neutralization of acidic black ACE product as a comparative sample
(1) Coupling reaction 1
Stirring 2-amino-4-nitrophenol in hydrochloric acid solution uniformly. Under the acidic condition, adding water into sodium nitrite to prepare nitrous acid solution, adding hydrochloric acid to control pH to be less than 1, and reacting for 1 hour. Dissolving N-phenyl-J acid in sodium hydroxide solution to dissolve completely, adding reaction liquid, controlling pH value to be 9-9.5, reacting for two hours at 20 ℃, filtering to obtain filter cake, namely a conjugate 1, wherein the filtrate is waste water, and feeding the waste water into a sewage treatment net.
(2) Preparation of chromizing agent solution
Adding water into a reaction bottle, adding chromium oxide and formic acid under stirring, heating to 50 ℃, keeping the temperature, stirring to dissolve all the components, adding salicylic acid, and stirring for 30 minutes for later use.
(3) Complexation reaction 1
Adding water into a reaction bottle, heating to 50 ℃, adding a conjugate 1, adjusting the pH to be 2 by hydrochloric acid, adding 98% sulfuric acid, heating to 115 ℃, carrying out heat preservation reaction for 6 hours, cooling and filtering to obtain a complex 1 for later use. The filtrate is waste water and enters a sewage treatment net.
(3) Coupling reaction 2
Preparation of 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid solution: dissolving 6-nitro in water, stirring for 30 min, slowly adding liquid alkali, and adjusting pH=3.5-4.0; preparation of 2-naphthol solution: adding 2-naphthol into alkaline solution, heating to 50-60 ℃, stirring for dissolution, adding into reaction solution, controlling pH=10-10.5, and reacting at 45 ℃ for two hours to obtain a solution of the conjugate 2.
(4) Complexation reaction 2
Adding the solution of the conjugate 2 into the complex 1, heating to 90 ℃, controlling the pH value to be 7.0-7.5, sampling after reacting for 1 hour, performing lamellar analysis, and if the solution is not required to be chromized by 1 little excess, stirring and reacting for 3 hours, adding sodium hydroxide to the pH value to be 8.0, and reacting for 30 minutes. Drying
The waste water produced in the reaction process contains acid, alkali, salt, halogen, nitro-compound, dye and intermediates thereof, heavy metal mercury, cadmium, chromium and the like, has complex components and toxicity, is uniformly recovered into a sewage treatment net, and is uniformly discharged after reaching the discharge standard by selecting a proper process for sewage treatment.
Dye fastness test
(1) Preparing a fabric: 2g of pure Bai Jinguan cloth is soaked in hot water at 80 ℃ for 10min and then put into hot water for standby.
(2) Dye dissolution:
transferring 5ml of acetic acid solution by a pipette to dilute 0.5g of the green black dye prepared in the examples 1,2 and 3 and the dye prepared in the comparative example 1 respectively, putting into 500ml volumetric flasks to fix volume and diluting to scale;
then respectively putting the soaked pure white nylon cloth, adding 10ml of 5% anhydrous sodium sulphate and 0.5m1 acetic acid buffer solution, heating to 98 ℃, preserving heat for 1 hour, cooling to 60 ℃, taking out the fabric, rinsing with clean water, putting into a 60℃ oven for drying, obtaining example product 1 and comparative example printing and dyeing product, and performing color light detection.
(3) And (3) measuring by an instrument: the determination was made using a Datacolor colorimeter.
(4) Determination result: and judging the result according to the LAB and the CMC.
(5) Analysis of results:
the national standard fastness test standards were applied to the example 1,2, 3 and comparative example 1, respectively, for the bleached and dyed nylon cloths: wherein, the soaping adopts the method in GB/T3921-2008, the dry and wet friction adopts the method in GB/T3920-2008, the kier adopts the method in GB/T7765-1997, the sun-drying adopts the method in GB/T8426-1998, the alkali-proof sweat adopts the method in GB/T3922-1995, the chlorination-proof adopts the method in GB/T8441-1998, and the detection results are shown in the following table:
TABLE 1
| Dye batch | Soaping process | Dry massage | Wet massage | Boiling woolen cloth | Sun-drying | Alkali sweat resistant | Chlorination resistance |
| Example 1 | 4 | 4 | 3 | 2-3 | 5-6 | 4-5 | 4-5 |
| Example 2 | 3-4 | 4-5 | 3 | 2-3 | 6 | 4 | 4-5 |
| Example 3 | 4 | 4-5 | 3-4 | 2-3 | 6 | 4-5 | 4-5 |
| Comparative example 1 | 3-4 | 4 | 3 | 2-3 | 5-6 | 4 | 4-5 |
And the test of the dyed fabrics of examples 1 and 2 shows that Da < 0, showing that the color is greenish, dc > 0 represents the color is bright, and CMCDE.ltoreq.0.75 shows that the dyed fabrics of examples 1 and 2 are green by the total color difference test, thereby showing that the dyed fabrics of examples 1 and 2 are significantly bright green.
The dye prepared by using the embodiment 1,2 and 3 has little waste water after the preparation is finished, and a small amount of generated waste water has low contents of acid, alkali, salt and the like, is easy to treat, can effectively reduce the cost of waste water treatment in the process of dye production in factories, and saves the production cost.
By combining the detection data and the results in table 1, the dye prepared in examples 1,2 and 3 is used for bleaching and dyeing the nylon cloth, and the obtained product is more stable in terms of cleaning, friction, high-temperature boiling, sun drying, alkali sweat resistance and chlorination resistance compared with comparative example 1, which shows that the green black dye prepared by the method can meet the requirements on dyeing and printing of wool, silk, nylon, leather, paper and other residual materials, has good dyeing effect and stable property, is not easy to fade, has good color fixing property even under the conditions of high temperature, strong illumination, strong alkali and strong chlorine, and does not influence the quality of the dyed product.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A green black dye, characterized in that: has the structure of formula (1):
2. a preparation method of a green-light black dye is characterized by comprising the following steps: the reaction formula is as follows:
step one, diazotization reaction
Diazotization reaction 1: preparation of solution b
Diazotization reaction 2: preparation of g solution
Step two, coupling reaction
Coupling reaction 1:
coupling reaction 2:
step three, complexation reaction
Complexing reaction 1:
complexing reaction 2:
3. a method for preparing a green black dye according to claim 2, wherein: in the coupling reaction of the second step, a dispersing agent is added in addition to the reactants, wherein the dispersing agent is at least one of lignin and NNO.
4. A method for preparing a green black dye according to claim 2, wherein:
coupling reaction 1: c is added into b, the temperature is controlled at 8-12 ℃, the pH value is regulated to be less than 1, the reaction is carried out for one hour, the reaction solution is added into the solution a, the dispersing agent is added, the pH value is controlled to be 9.5-10.5, and the reaction is carried out for two hours, so that azo solution d is obtained;
complexing reaction 1: mixing azo solution d and solution e, and adjusting the pH value to be 1-2 by hydrochloric acid; adding a small amount of 98% sulfuric acid, sealing the reaction bottle, heating to 140 ℃, controlling the pressure to 300-400 kPa, reacting for 4 hours under heat preservation, and cooling to room temperature for standby to obtain a complex solution f;
coupling reaction 2: adding the solution h into the solution g, controlling the temperature at 35-50 ℃, adding a dispersing agent (lignin/NNO and the like), controlling the pH value to be 10-10.5, and reacting for two hours to obtain a coupling solution i;
complexing reaction 2: adding the solution i into the solution f, heating to 90 ℃, adding sodium hydroxide to pH=7.0-7.5, reacting for 1 hour, sampling for lamellar analysis, continuously stirring for 3 hours, adding sodium hydroxide for regulating to pH=8.0, reacting for 30 minutes, resampling for lamellar analysis, and obtaining a complex j after the reaction is finished;
and after the end point is qualified, adding hydrochloric acid to adjust the pH to be 7.5, and evaporating to dryness to obtain the green black acid dye.
5. A method for preparing a green black dye according to claim 2 or 4, wherein:
a, preparing a solution: dissolving N-phenyl-J acid in sodium hydroxide solution, controlling ph=8-10;
b, preparation of solution: uniformly stirring 2-amino-5-nitrophenol in a hydrochloric acid solution, and controlling the pH value to be 1-2;
c, preparation of solution: adding water into sodium nitrite to dissolve the sodium nitrite to prepare nitrous acid solution;
e, preparing a solution: adding water and formic acid into a reaction bottle to prepare a solution with the concentration of 50%, adding chromium oxide and NaOH solution under stirring, heating to 50 ℃, keeping the temperature, continuously stirring to dissolve the solution completely, and adding salicylic acid and stirring for 30 minutes;
g, preparation of solution: adding 6-nitro-1, 2-diazoxynaphthalene-4-sulfonic acid into water for dissolution, stirring for 30 minutes, slowly adding liquid alkali, and adjusting pH=3.5-4;
h, preparation of a solution: adding 2-naphthol into sodium hydroxide solution, heating to 50-60 ℃ and stirring uniformly to obtain 2-naphthol solution.
6. Use of a dye containing green black according to claim 1 in the dyeing and printing of wool, silk, nylon, leather, paper.
7. The green black dye prepared by the method of claim 2 is applied to the dyeing and printing process of wool, silk, chinlon, leather and paper.
8. The use of the green black dye according to claim 6 for dyeing nylon cloth, wherein: the nylon cloth is firstly placed in hot water for soaking for a period of time, then is transferred to warm water for soaking, after the dye is diluted, 10ml of 5% anhydrous sodium sulphate, 0.5m1 acetic acid buffer solution and soaked pure Bai Jinguan cloth are added, the temperature is raised to 98 ℃, the temperature is kept for 1 hour, the temperature is reduced to 60 ℃, the fabric is taken out and washed out by clean water, and then is put into a 60 ℃ oven for drying.
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