CN109575630B - Preparation method of reddish brown reactive dye - Google Patents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention relates to a preparation method of a reddish brown reactive dye, which comprises the following steps: 1) preparing an anthranilic acid diazonium salt; 2) acetyl J acid and ortho-ammoniaPerforming coupling reaction on diazobenzoate, performing hydrolysis reaction to remove acetyl to obtain coupling solution, 3) preparing chromium compound solution, performing complex reaction on the coupling solution and the chromium compound solution to obtain chromium complex solution, 4) performing primary condensation reaction on cyanuric chloride and β -aminoethanesulfonic acid to obtain primary condensation solution, 5) performing secondary condensation reaction on the primary condensation solution and the chromium complex solution to obtain the reddish brown reactive dye, wherein the process route is improved, the salting-out process is avoided, the prepared reddish brown reactive dye has good dyeing fastness and good solubility, the color change of the prepared printing paste within 48h is less than 2%, and free Cr is free6+Less than 2ppm of residue on the fabric, good compatibility with other dyes and chemicals, and good reproducibility of printing and dyeing.
Description
Technical Field
The invention relates to the field of preparation of reactive dyes, in particular to a preparation method of a reddish brown reactive dye.
Background
The metal complex dye refers to a dye having a specific structure and forming a metal complex with a metal complexing agent. Because the metal complex ions are introduced into the dye molecules, the dye can obtain certain deep chromatograms such as black, navy blue, reddish brown and the like, and can improve and enhance the fastness performance and the dyeing performance of the dye.
The metal complex dye contains most of chromium, copper, nickel, cobalt, iron and the like, and the used metal elements are first transition elements on the periodic table of the elements and contain a 3d empty orbit. The metal complex dyes are of a wide variety, mainly including: azo metal complex dyes, azo metal complex direct dyes, azo metal complex reactive dyes, azo metal complex ice dyes and the like. Among them, the azo metal complex dye accounts for the majority of the whole metal complex dye, and the application range is wide and not reached by other structure type metal complex dyes.
The invention patent application (CN 101519537A) discloses an asymmetric azo complex dye and a preparation method thereof, which comprises that an azo compound is taken as a main body, and a chromium complex is formed by a compound synthesized by para-amino azo sulfonic acid naphthalene, resorcinol and diazo onium naphthalene compounds.
The general formula of the asymmetric azo complex dye is shown as formula (I):
the invention patent application (CN 101044211A) discloses an azo metal complex dye. Is especially suitable for dip-dyeing synthetic polyamide fiber materials, and simultaneously, the dyed or printed products have good moisture resistance. The structural general formula of the dye is shown as formula (II):
with the enhancement of environmental awareness, not only higher and higher quality requirements are put forward for textiles, but also fewer and fewer three wastes are required in the process of manufacturing the textiles. At present, a salting-out procedure exists in the production process of the azo metal complex dye, and high-chroma salt-containing wastewater is generated in the salting-out procedure. In addition, the product obtained by the existing preparation process has low solubility, withered color light, poor color fixing capability and low yield, and is easy to hydrolyze after being prepared into color paste in printing and dyeing processing, the color on the fabric of the textile is not deep enough, and the important point is that the residual Cr exceeds the standard.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a reddish brown reactive dye, which avoids a salting-out process by improving a process route; in addition, the prepared red brown reactive dye has good color fastness and good solubility, the color ratio change of the prepared printing paste within 48 hours is less than 2 percent, and free Cr is6+Less than 2ppm of residue on the fabric, good compatibility with other dyes and chemicals, and good reproducibility of printing and dyeing.
The technical scheme provided by the invention is as follows:
a preparation method of a reddish brown reactive dye comprises the following steps:
1) preparing an anthranilic acid diazonium salt;
2) acetyl J acid and anthranilic acid diazonium salt are subjected to coupling reaction, and then hydrolysis reaction is carried out to remove acetyl to obtain coupling liquid;
3) preparing a chromium compound solution, and carrying out a complex reaction on the coupling solution and the chromium compound solution to obtain a chromium complex solution;
4) cyanuric chloride and β -aminoethanesulfonic acid are subjected to primary condensation reaction to obtain primary condensation liquid;
5) and carrying out secondary condensation reaction on the primary condensation liquid and the chromium complex liquid to obtain the reddish brown reactive dye.
The structural formula of the red brown reactive dye is as follows:
in the invention, acetyl J acid is adopted to replace J acid, so that the generation of a byproduct (IV) by coupling the o-aminobenzoic acid diazonium salt and an amino ortho-position can be avoided, and the generation of the byproduct (V) by reacting impurity isomer gamma acid in the J acid raw material with the o-aminobenzoic acid diazonium salt can also be avoided.
As the coupling method of acetyl J acid and anthranilic acid diazonium salt is introduced, impurity byproducts generated in the process are avoided, and the process of chromophore salting-out can be omitted.
According to the invention, β -aminoethanesulfonic acid is used for replacing para-ester, because the dye with a para-ester structure contains ethyl sulfone sulfate ester groups, the groups can be hydrolyzed under an alkaline condition to generate a hydrolyzed dye with hydroxyethyl sulfone groups, so that the color fixing capability is lost, and simultaneously, the introduction of β -aminoethanesulfonic acid improves the solubility of the dye, and is more beneficial to the preparation of printing paste.
According to the invention, a synthetic route of firstly condensing cyanuric chloride and β -aminoethanesulfonic acid and then secondarily condensing the cyanuric chloride and chromium complex liquid is selected, so that the color fixation rate of the reddish brown reactive dye can be improved, if the chromium complex liquid is condensed with cyanuric chloride, the dye in the formula (VI) is obtained, and then the dye is secondarily condensed with β -aminoethanesulfonic acid.
As the dye in the formula (VI) belongs to an X type (dichloro-s-triazine structure), under the temperature and the pH value of secondary condensation, one chlorine in the dichloro-s-triazine structure can react with β -aminoethanesulfonic acidCondensation reaction, may also be embodied as OH-Partial hydrolysis occurs, the two have a competitive relationship, the dye after hydrolysis loses the color fixing ability, the problems of staining and the like are easily caused in the post-treatment washing process of printing and dyeing enterprises, and the color fixing rate is reduced.
The preparation of the anthranilic acid diazonium salt in the step 1) comprises the following steps: dissolving anthranilic acid in hydrochloric acid solution, adding ice for cooling after dissolving, dropwise adding sodium nitrite solution, controlling the dropwise adding temperature and the reaction temperature below 5 ℃, reacting for 60-90min, and eliminating excessive sodium nitrite by sulfamic acid to obtain anthranilic acid diazonium salt solution.
The coupling reaction in the step 2) of the invention comprises the following steps: dissolving acetyl J acid into neutral solution with liquid alkali, cooling to 8-12 deg.C, adding sodium bicarbonate, stirring, slowly adding diazo anthranilate, maintaining pH at 7.5-8.5, and reacting at 10-15 deg.C for 2-4 h.
The molar ratio of the baking soda to the acetyl J acid is (1.0-1.5): 1. The baking soda is used for neutralizing HCl generated in the coupling reaction, so that the pH value of the coupling reaction is maintained.
The molar ratio of the anthranilic acid diazonium salt to the acetyl J acid is (0.95-1.05): 1.
The hydrolysis reaction in the step 2) comprises the following steps: heating the chromophore solution obtained by the coupling reaction to 90-95 ℃, adding liquid alkali, maintaining the temperature at 90-95 ℃ for reaction, sampling and detecting the end point, wherein the amino value yield of more than 99 percent is the hydrolysis end point.
The hydrolysis reaction was as follows:
the preparation of the chromium compound solution in the step 3) comprises the following steps: preparing a solution of water, glucose and glacial acetic acid, dripping 50-60 wt% of sodium dichromate solution at the temperature of 85-95 ℃, and then refluxing at the temperature of 100-105 ℃ for reduction reaction to obtain the sodium dichromate.
The mass ratio of the sodium dichromate, the glucose and the glacial acetic acid is 1 (0.3-0.5) to 0.8-1.2.
The complexation reaction in step 3) in the invention comprises the following steps: adjusting the pH of the coupling solution to 7.0-7.5 by using glacial acetic acid, keeping the temperature rising to 95-98 ℃ after the coupling solution is stabilized for 20-40min, adding a chromium compound solution, maintaining the pH of the coupling solution to 4-6 by using 15-25 wt% of sodium carbonate solution, and reacting for 4-6h to obtain the chromium complex solution.
The chromium complex solution is continuously adjusted to pH of 10.0-10.5 by trisodium phosphate, reacted for 2-4h, cooled to 45-55 ℃, filtered to remove impurities, and the filtrate is collected. In the process, trisodium phosphate is added to remove free chromium, so that the free chromium can reach the Oeko-Tex standard.
In the step 4), the primary condensation reaction comprises dispersing and pulping cyanuric chloride in ice water, adding β -aminoethanesulfonic acid, adjusting pH to 6.5-7.5 with 15-25 wt% of sodium carbonate solution, and reacting for 3-5h at 5-8 ℃.
The secondary condensation reaction in the step 5) comprises the following steps: and quickly adding the primary condensation liquid into the chromium complex liquid, maintaining the pH value of the solution at 6.0-7.0 by using 15-25 wt% of soda ash solution, and reacting for 6-10 h. Preferably, the dye raw pulp obtained by the secondary condensation reaction is standardized with a dispersant NNO and a dispersant MF, and is spray-dried to obtain a reddish brown reactive dye finished product.
Compared with the prior art, the invention has the beneficial effects that:
(1) the process effectively shortens the generation period to 48 h; the manufacturing process has no salting-out process, and does not generate high-chroma high-COD salt-containing wastewater.
(2) The reddish brown reactive dye prepared by the process has better solubility of more than 200g/L, the change of the color yield of printing paste within 48h is less than 2%, the dye has higher fixation rate, good printing reproducibility and excellent fastness properties, and the free chromium remained on the printed fabric can reach the Oeko-Tex standard and meets the requirement of environmental protection.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
(1) Adding 1500L of bottom water into a diazo kettle, heating to 35 ℃, dissolving 230 kg of 30 wt% hydrochloric acid and 137.2 kg of anthranilic acid, stirring for 30 minutes to dissolve, adding ice to cool, dropwise adding 230 kg of 30 wt% sodium nitrite solution, controlling the dropwise adding temperature and the reaction temperature to be below 5 ℃, controlling the reaction time to be 60-90 minutes, and eliminating excessive sodium nitrite by using sulfamic acid to obtain the anthranilic acid diazo solution.
(2) Adding 1500L of bottom water into a coupling kettle, adding 281 kg of acetyl J acid, stirring for 20 minutes, dissolving the acetyl J acid by using 30 wt% of liquid alkali, controlling the pH value to be 7.5-8.5, adding 1200 kg of ice and 100 kg of baking soda after the acetyl J acid is dissolved, stirring for a moment, slowly adding the prepared anthranilic acid diazonium salt solution, maintaining the pH value to be 7.5-8.5, and reacting at the temperature of 10-15 ℃ for 3 hours to obtain a color base solution.
(3) And (3) at the coupling end point, heating the chromophore solution obtained by the coupling reaction to 90 ℃, adding 550 kilograms of 30 wt% of liquid alkali, maintaining the temperature at 90-95 ℃ for reaction for 4 hours, sampling, detecting the end point, and taking the amino value yield of more than 99% as the hydrolysis end point to obtain the coupling liquid.
(4) Preparing a chromium compound solution: 750L of bottom water is added into the reaction kettle, 920 kg of sodium dichromate is added under stirring, and the solution is dissolved clearly to obtain 55 wt% of sodium dichromate solution. 700L of bottom water, 360 kg of glucose and 900 kg of glacial acetic acid are added into the other reaction kettle, sodium chromate solution is added dropwise at 90 ℃ for about 2 hours, and reduction reaction is carried out under reflux at 100-105 ℃ for 2 hours to obtain 3630 kg of chromium compound solution.
(5) And (3) after the hydrolysis is finished, adjusting the pH value of the coupling solution in the step (3) to 7.0-7.5 by using glacial acetic acid, stabilizing for 30 minutes, continuing to heat to 95-98 ℃, adding 202 kg of freshly prepared chromium compound solution, maintaining the pH value in a range of 4-6 by using 20 wt% of soda ash solution, reacting for 5 hours, adjusting the pH value to 10.0-10.5 by using trisodium phosphate after the complexation is finished, reacting for 3 hours, starting cooling water, cooling to 50 ℃, filtering to remove impurities, and collecting filtrate to obtain the 1:2 chromium complex solution.
(6) 500L of bottom water and 500 kg of ice are added into a primary condensation kettle, 210 kg of cyanuric chloride is added into the ice water for dispersion and pulping for 1 hour, 140 kg of β -aminoethanesulfonic acid powder is added, the pH value is adjusted to 6.5-7.5 by 20 wt% of sodium carbonate solution, and the temperature is maintained at 5-8 ℃ for reaction for 4 hours, so that primary condensation liquid is obtained.
(7) And quickly adding the primary condensation liquid into the 1:2 chromium complex liquid, simultaneously maintaining the pH value of the primary condensation liquid to be 6.0-7.0 by using 20 wt% of soda ash solution, reacting for 8 hours to obtain primary dye stock, standardizing the primary dye stock with 150 kg of NNO and 230 kg of MF (dispersant), and performing spray drying to obtain 1750 kg of reddish brown reactive dye finished product.
Comparative example 1
(1) Adding 1500L of bottom water into a diazo kettle, heating to 35 ℃, dissolving 230 kg of 30 wt% hydrochloric acid and 137.2 kg of anthranilic acid, stirring for 30 minutes to dissolve, adding ice to cool, dropwise adding 230 kg of 30 wt% sodium nitrite solution, controlling the dropwise adding temperature and the reaction temperature to be below 5 ℃, controlling the reaction time to be 60-90 minutes, and eliminating excessive sodium nitrite by using sulfamic acid to obtain the anthranilic acid diazo solution.
(2) Adding 1500L of bottom water into a coupling kettle, adding 281 kg of acetyl J acid, stirring for 20 minutes, dissolving the acetyl J acid by using 30 wt% of liquid alkali, controlling the pH value to be 7.5-8.5, adding 1200 kg of ice and 100 kg of baking soda after the acetyl J acid is dissolved, stirring for a moment, slowly adding the prepared anthranilic acid diazonium salt solution, maintaining the pH value to be 7.5-8.5, and reacting at the temperature of 10-15 ℃ for 3 hours to obtain a color base solution.
(3) And (3) at the coupling end point, heating the chromophore solution obtained by the coupling reaction to 90 ℃, adding 550 kilograms of 30 wt% of liquid alkali, maintaining the temperature at 90-95 ℃ for reaction for 4 hours, sampling, detecting the end point, and taking the amino value yield of more than 99% as the hydrolysis end point to obtain the coupling liquid.
(4) Preparing a chromium compound solution: 750L of bottom water is added into the reaction kettle, 920 kg of sodium dichromate is added under stirring, and the solution is dissolved clearly to obtain 55 wt% of sodium dichromate solution. 700L of bottom water, 360 kg of glucose and 900 kg of glacial acetic acid are added into the other reaction kettle, sodium chromate solution is added dropwise at 90 ℃ for about 2 hours, and reduction reaction is carried out under reflux at 100-105 ℃ for 2 hours to obtain 3630 kg of chromium compound solution.
(5) And (3) after the hydrolysis is finished, adjusting the pH value of the coupling solution in the step (3) to 7.0-7.5 by using glacial acetic acid, stabilizing for 30 minutes, continuing to heat to 95-98 ℃, adding 202 kg of freshly prepared chromium compound solution, maintaining the pH value in a range of 4-6 by using 20 wt% of soda ash solution, reacting for 5 hours, adjusting the pH value to 10.0-10.5 by using trisodium phosphate after the complexation is finished, reacting for 3 hours, starting cooling water, cooling to 10 ℃, filtering to remove impurities, and collecting filtrate to obtain the 1:2 chromium complex solution.
(6) Adding 500L of bottom water and 500 kg of ice into a primary condensation kettle, adding 210 kg of cyanuric chloride, dispersing and pulping in the ice water for 1 hour, adding 1:2 chromium complex solution, maintaining the temperature at 5-8 ℃, maintaining the pH at 4.5-5.5 with sodium bicarbonate after the addition, and reacting for 6 hours to obtain primary condensation solution.
(7) Adding 136 kg of β -aminoethanesulfonic acid powder into the primary condensation solution, heating to 45 ℃, adjusting the pH value to 7.0-8.0 by using 20 wt% of soda solution, maintaining the temperature at 45-50 ℃ for reacting for 6 hours to obtain dye raw pulp, standardizing with 150 kg of NNO as a dispersing agent and 230 kg of MF as a dispersing agent, and performing spray drying to obtain 1680 kg of a reddish brown reactive dye finished product.
Comparative example 2
(1) Adding 1500L of bottom water into a diazo kettle, heating to 35 ℃, dissolving 230 kg of 30 wt% hydrochloric acid and 137.2 kg of anthranilic acid, stirring for 30 minutes to dissolve, adding ice to cool, dropwise adding 230 kg of 30 wt% sodium nitrite solution, controlling the dropwise adding temperature and the reaction temperature to be below 5 ℃, controlling the reaction time to be 60-90 minutes, and eliminating excessive sodium nitrite by using sulfamic acid to obtain the anthranilic acid diazo solution.
(2) Adding 1500L of bottom water into a coupling kettle, adding 239 kg of J acid, stirring for 20 minutes, dissolving the J acid by using 30 wt% of liquid alkali, controlling the pH value to be 7.5-8.5, adding 1200 kg of ice and 100 kg of baking soda after dissolving, stirring for a while, slowly adding the prepared anthranilic acid diazonium salt solution, keeping the pH value to be more than 7.5, and reacting for 3 hours at the temperature of 10-15 ℃ to obtain a coupling solution.
(3) After the coupling end point is reached, the temperature is raised to 90 ℃, the volume is about 7000L, 1500 kg of sodium chloride is added for salting out, the stirring speed is maintained for 15 r/min after the crystallization is clear, the mixture is slowly stirred for 2 hours and then is filtered by a membrane filter press, and about 1100 kg of filter cake is obtained.
(4) Adding 1500L of bottom water into a complexing kettle, heating to 85-90 ℃, adjusting the pH value to 8.0-8.5, further heating to 98-100 ℃, adding 25 kg of salicylic acid, uniformly dropwise adding a chromium sulfate solution within 2 hours (preparation method: 160 kg of chromium sulfate powder is dissolved by 500L of hot water), simultaneously maintaining the pH value within 4.5-6.5 by 10 wt% of soda ash solution, reacting for 12 hours, starting cooling water to cool to 10 ℃ after the complexing end point is reached, and obtaining the 1:2 chromium complexing liquid.
(5) Adding 500L of bottom water and 500 kg of ice into a primary condensation kettle, adding 210 kg of cyanuric chloride, dispersing and pulping in the ice water for 1 hour, adding 1:2 chromium complex solution, maintaining the temperature at 5-8 ℃, maintaining the pH at 4.5-5.5 with sodium bicarbonate after the addition, and reacting for 6 hours to obtain primary condensation solution.
(6) 295 kg of para-ester powder is added into the primary condensation solution, the temperature is raised to 52 ℃, baking soda is used for maintaining the pH value between 5.5 and 6.0, the temperature is maintained between 52 and 55 ℃, the reaction is carried out for 8 hours, the dye raw stock is obtained, the volume is about 6500L, 1200 kg of sodium chloride is added, the raw stock is immediately fed into a membrane filter press after the crystal is clear, and about 1400 kg of filter cake is obtained.
(7) 2500L of commercialized kettle bottom water is added with filter cakes for pulping, dispersing and dissolving, then 320 kg of anhydrous sodium sulphate is standardized and spray-dried to obtain 1320 kg of reddish brown reactive dye finished product.
Performance testing
As can be seen from the processes of the embodiment 1 and the comparative examples 1-2, the quality of the product obtained by the method is better than that of the product obtained by the comparative examples 1 and 2. Does not generate high-chroma and high-COD salt-containing wastewater, the production process is more environment-friendly and green, and the production period is shortened from 72 hours of the traditional process to 48 hours.
The yield of the product is greatly improved, compared with the comparative example 2, the yield of the product in the embodiment 1 is improved by 32.57%, the comprehensive cost is reduced by 18.92%, and the product has more competitive advantages in the market.
Comparing the red-brown reactive dye samples prepared in example 1, comparative example 1 and comparative example 2, it can be seen that the performance of the red-brown reactive dye prepared in example 1 is obviously better than that of comparative examples 1 and 2.
Table 1 compares solubility, integra values at different depths, shade and fixation (shade is based on the samples made in the examples). Table 2 compares the residual content of extractable chromium metal on the printed fabrics. Table 3 compares the fastnesses.
TABLE 1
TABLE 2
Remarking: the extractable heavy metal chromium of the Oeko-Tex standard is less than or equal to 2mg/kg, and the extractable heavy metal hexavalent chromium is less than or equal to 0.5mg/kg
TABLE 3
Claims (7)
1. A preparation method of a reddish brown reactive dye is characterized by comprising the following steps:
1) preparing an anthranilic acid diazonium salt;
2) acetyl J acid and anthranilic acid diazonium salt are subjected to coupling reaction, and then hydrolysis reaction is carried out to remove acetyl to obtain coupling liquid; the coupling reaction comprises the following steps: dissolving acetyl J acid into neutral solution with liquid alkali, cooling to 8-12 deg.C, adding sodium bicarbonate, stirring, slowly adding diazo anthranilate, maintaining pH at 7.5-8.5, and reacting at 10-15 deg.C for 2-4 h; the hydrolysis reaction comprises the following steps: heating the chromophore solution obtained by the coupling reaction to 90-95 ℃, adding liquid alkali, maintaining the temperature at 90-95 ℃ for reaction, sampling and detecting the end point, wherein the hydrolysis end point is the amino value yield of more than 99%;
3) preparing a chromium compound solution, and carrying out a complex reaction on the coupling solution and the chromium compound solution to obtain a chromium complex solution;
4) cyanuric chloride and β -aminoethanesulfonic acid are subjected to primary condensation reaction to obtain primary condensation liquid, wherein the primary condensation reaction comprises the steps of dispersing and pulping cyanuric chloride in ice water, adding β -aminoethanesulfonic acid, adjusting the pH value to 6.5-7.5 by using 15-25 wt% of sodium carbonate solution, and reacting for 3-5 hours at the temperature of 5-8 ℃;
5) carrying out secondary condensation reaction on the primary condensation liquid and the chromium complex liquid to obtain a reddish brown reactive dye;
the structural formula of the reddish brown reactive dye is as follows:
2. the method for preparing the reddish brown reactive dye according to claim 1, wherein the molar ratio of the baking soda to the acetyl J acid is (1.0-1.5): 1; the molar ratio of the anthranilic acid diazonium salt to the acetyl J acid is (0.95-1.05): 1.
3. The method for preparing the reddish brown reactive dye according to claim 1, wherein the preparing the chromium compound solution in the step 3) comprises: preparing a solution of water, glucose and glacial acetic acid, dripping 50-60 wt% of sodium dichromate solution at the temperature of 85-95 ℃, and then refluxing at the temperature of 100-105 ℃ for reduction reaction to obtain the sodium dichromate.
4. The preparation method of the reddish brown reactive dye according to claim 3, wherein the mass ratio of the sodium dichromate to the glucose to the glacial acetic acid is 1 (0.3-0.5) to (0.8-1.2).
5. The method for preparing the reddish brown reactive dye according to claim 1, wherein the complexing reaction in the step 3) comprises: adjusting the pH of the coupling solution to 7.0-7.5 by using glacial acetic acid, keeping the temperature rising to 95-98 ℃ after the coupling solution is stabilized for 20-40min, adding a chromium compound solution, maintaining the pH of the coupling solution to 4-6 by using 15-25 wt% of sodium carbonate solution, and reacting for 4-6h to obtain the chromium complex solution.
6. The preparation method of the reddish brown reactive dye according to claim 5, wherein the chromium complex solution is continuously adjusted to pH 10.0-10.5 with trisodium phosphate, reacted for 2-4h, cooled to 45-55 ℃, filtered to remove impurities, and the filtrate is collected.
7. The method for preparing the reddish brown reactive dye according to claim 1, wherein the secondary condensation reaction in the step 5) comprises: and quickly adding the primary condensation liquid into the chromium complex liquid, maintaining the pH value to be 6.0-7.0 by using 15-25 wt% of sodium carbonate solution, and reacting for 6-10 h.
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| JPS59159855A (en) * | 1983-03-03 | 1984-09-10 | バスフ アクチェン ゲゼルシャフト | Sulfonamide group-free and amino group-free metal complex dye |
| CN1267506C (en) * | 2001-10-17 | 2006-08-02 | 克莱里安特财务(Bvi)有限公司 | 1:2 metal complex dyes, their compositions, their production and their use |
| KR100954509B1 (en) * | 2004-10-19 | 2010-04-27 | 훈츠만 어드밴스트 머티리얼스(스위처랜드) 게엠베하 | Reactive dyes, their preparation and their use |
| CN101519537A (en) * | 2008-02-26 | 2009-09-02 | 文擘科技股份有限公司 | Asymmetric azo complex dye and manufacturing method thereof |
| TWI500707B (en) * | 2009-01-21 | 2015-09-21 | Huntsman Adv Mat Switzerland | Reactive dyes, their preparation and their use |
| CN102337040A (en) * | 2011-07-20 | 2012-02-01 | 青岛双桃精细化工（集团）有限公司 | Preparation method of neutral metal complex dye |
| CN105585874B (en) * | 2015-12-28 | 2017-07-04 | 浙江劲光实业股份有限公司 | A kind of active gray dyes and preparation method thereof |
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