CN101585973B - Method for synthesizing acid red R3G by utilizing phase transfer catalysts - Google Patents
Method for synthesizing acid red R3G by utilizing phase transfer catalysts Download PDFInfo
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Abstract
The invention provides an acid red R3G preparation method with no process wastewater, high product yield, good product quality and low cost. By adding an N-methyl pyrrolidone phase-transfer catalyst in reaction, raising the temperature of two-step condensation reaction to between 50 and 65 DEG C and adjusting pH between 7.0 and 10.5, the preparation method raises the conversion rate of the reaction from 90 percent to more than 98 percent, and enables color light strength and other application performance indexes of one-time synthesized raw stock dye during production to reach the level of qualified products.
Description
Technical field
The present invention relates to the matching stain technical field, relate in particular to a kind of method of utilizing the phase-transfer catalyst synthesizing acid red R 3 G.
Background technology
The acid red R 3 G dyestuff has the distinguishing features such as application performance bright in colour is excellent, easy to use, and suitability is strong, and manufacturer production is all arranged both at home and abroad, and the preparation method of this dyestuff is open in the patent application of CN 101125964A at publication number.
In the above-mentioned patent documentation of production neutralization at present, disclosed preparation method adopts the main raw material process for purification to reach magma spraying drying purpose, but in the refining J acid by using process, generation contains the sour by-product impurity organic waste water that is situated between and is difficult to administer, and loss 5%-8% is situated between sour in treating process.Expense and the sour economic factors of losing that is situated between because restriction and the three wastes of ecotope are processed restrict the competitive power of this product on market.So the present invention finds to affect the reaction conversion ratio of quality product principal element in two step condensation building-up processes by research, the present invention has solved above-mentioned technical problem by improved acid red R 3 G preparation method.
Summary of the invention
The present invention will solve in two step condensation courses the water insoluble formation solid granular of main raw material amino dodecane, and to make reaction system be the low technical problem that has affected product coloured light and application performance of solid-liquid two phase reaction, reaction conversion ratio.For solving the problems of the technologies described above, the invention provides a kind of preparation method that must measure the acid red R 3 G high, that quality good, cost is low without processing wastewater, product, this preparation method is by adding N methyl-2-pyrrolidone phase-transfer catalyst and two step setting-up point being increased to 50-65 ℃ in reaction, pH is adjusted to 7.0-10.5, the transformation efficiency of its reaction is increased to more than 98% by 90%, and the magma dye shade intensity that in production process, single sintering is completed and other application performance index reach the level of qualified product.
Particularly, the invention provides a kind of method of utilizing phase-transfer catalyst to produce acid red R 3 G, the method comprises a step condensation, diazotization, coupling, two step condensation and finished products, it is characterized in that in two step condensation courses, amino dodecane being added N methyl-2-pyrrolidone phase-transfer catalyst after with dissolve with ethanol, in two step condensations, temperature of reaction is 50-65 ℃, and pH is 7.0-10.5.
Particularly, body of the present invention provides a kind of method of utilizing the phase-transfer catalyst synthesizing acid red R 3 G, and the method comprises the steps:
F) a step condensation: add in frozen water cyanuric chloride in 0-10 ℃ stir 10 minutes after, slowly add the acid that is situated between, finishing rear use 10% sodium carbonate solution, to transfer pH be 3.0-6.5, reacted with this understanding 4-5 hour to get a step condensated liquid;
G) diazotization: add P-aminoazobenzene-4-sulfonic acid in water, be warming up to 55-65 ℃, adjusting pH with 30% sodium hydroxide solution is 7.5-8.5, all add Sodium Nitrite to mix after dissolving, then above-mentioned mixed solution was added the aqueous hydrochloric acid for preparing in 2-3 hour, keeping temperature is 10-20 ℃, guarantee that wherein Sodium Nitrite is excessive, be that potassium iodide starch paper is blueness, it is blue that congo-red test paper is, and reacted with this understanding 1-2 hour to get diazo liquid;
H) coupling: diazo liquid is added in primary condensation liquid, and transferring pH with 10% sodium carbonate solution is 6-7, and guarantees temperature lower than 15 ℃ with frozen water, and reacts with this understanding 2-3 hour, gets coupling solution;
I) two the step condensations: with amino dodecane with dissolve with ethanol after, add N methyl-2-pyrrolidone phase-transfer catalyst to mix, then add above-mentioned coupling solution, chuck is risen to 50-65 ℃ after stirring, and be 7.0-10.5 with 10% sodium carbonate solution accent pH, reacted with this understanding 5-8 hour to get two step condensated liquids;
J) finished products: two step condensated liquids are adjusted to required product intensity with Sodium sulfate anhydrous.min(99), and then spraying drying directly is packaged to be finished product.
The method of the acid red R 3 G of above-mentioned production of the present invention is compared with existing preparation method; finished product must be measured and improve more than 8%; and the waste water of having avoided refining J acid by using to produce; having saved main raw material is situated between sour; shorten man-hour, improved the economic benefit of product, strengthened product market competitiveness; stop the discharging of processing wastewater, protection of the environment has been played very large promoter action.The acid red R 3 G that preparation method of the present invention produces has good performance, and coloured light is bright-coloured, and solubleness is high, and every fastness is good, especially dyeing nylon is had good dye uptake and degree of fixation, has splendid enhancing rate.
Embodiment
Below by example, the present invention is described in detail, these embodiment just are used for explaining technical scheme of the present invention, are not that the present invention is formed any restriction.
Particularly, the preparation method's of acid red R 3 G specific embodiment is as follows:
Example 1
A) a step condensation: add end water 100Kg in pot, add trash ice 300Kg, temperature 0-3 ℃, add cyanuric chloride 50Kg to stir after 10 minutes, add the sour 70.11Kg that is situated between, finishing rear pH is 2.1, and then transferring pH with 10% sodium carbonate solution is 3.0-5.0, be to react 4 hours under 0-5 ℃ in temperature, get a step condensated liquid.
B) diazotization: add end water 600Kg in pot, add P-aminoazobenzene-4-sulfonic acid 80.11Kg again, be warming up to 55-65 ℃, adjusting pH with 30% sodium hydroxide solution is 7.5, add Sodium Nitrite 18.87Kg to mix 20 minutes, rear use time of 2 hours that stirs adds aqueous hydrochloric acid, keeps 15-20 ℃ of kettle temperature with trash ice, finishes to keep Sodium Nitrite excessive, be that potassium iodide starch paper is blueness, it is blue that congo-red test paper is, and reacted with this understanding 2 hours, gets diazo liquid.Wherein the compound method of aqueous hydrochloric acid is to add end water 100Kg in pot, then adds hydrochloric acid 79.2Kg, then adds trash ice 100Kg.
C) coupling: diazo liquid is added a step condensated liquid, then with trash ice insulation degree lower than 15 ℃, be then 6-7 with 10% sodium carbonate solution accent pH, reacted with this understanding the coupling solution until diazo liquid disappears to get 3 hours.
D) two step condensations: add N methyl-2-pyrrolidone 20.79Kg after in a barrel, amino dodecane 48.9Kg being dissolved with ethanol 30.2Kg, add after stirring and stir in coupling solution after 5 minutes with 50-55 ℃ of chuck intensification, and be 9.5-10.5 with 10% sodium carbonate adjustment pH simultaneously, reacted with this understanding 5-8 hour to get two step condensated liquids.
E) finished products: two step condensated liquids are adjusted to required product intensity with Sodium sulfate anhydrous.min(99), and then spraying drying directly is packaged to be finished product.
Example 2
A) a step condensation: add end water 100Kg in pot, add trash ice 300Kg, temperature 3-5 ℃, add cyanuric chloride 50Kg to stir after 10 minutes, add the sour 70.11Kg that is situated between to finish rear pH=2.1 and transfer pH=3-5 with 10% sodium carbonate solution, under this medium, temperature 0-5 ℃ was reacted 4-5 hour.
B) diazotization: add end water 600Kg to add P-aminoazobenzene-4-sulfonic acid 80.11Kg in pot again, be warming up to 55-65 ℃, adjusting pH with 30% sodium hydroxide solution is 7.5, adds Sodium Nitrite 18.87Kg to mix 20 minutes evenly rear standby.
C) another the pot in add end water 100Kg to add hydrochloric acid 79.2Kg to add again trash ice 100Kg after, above-mentioned mixed solution was added with about 2 hours, keep 15-20 ℃ of kettle temperature with trash ice simultaneously, finish and keep Sodium Nitrite excessive, be that potassium iodide starch paper is blueness, it is blue that congo-red test paper is, and reacted with this understanding 1 hour, gets diazo liquid.
D) coupling: after a step condensation is completed, diazo liquid is once added, lower than 15 ℃, finishing rear use 10% sodium carbonate solution accent pH is 6-7, reacts with this understanding 2 hours until diazo liquid disappears, and gets coupling solution with trash ice insulation degree.
E) two the step condensations: in one barrel with amino dodecane 48.9Kg, after adding N methyl-2-pyrrolidone 20.79Kg to stir all after ethanol 30.2Kg dissolving, add coupling solution, stir and be warming up to 55-60 ℃ with chuck after 5 minutes, and be 7.0-7.5 with 10% sodium carbonate adjustment pH simultaneously, reacted with this understanding 5-8 hour, and got two step condensated liquids.
F) finished products: two step condensated liquids are adjusted to required product intensity with Sodium sulfate anhydrous.min(99), and then spraying drying directly is packaged to be finished product.
Example 3
A) a step condensation: add end water 100Kg in pot, add trash ice 300Kg, temperature 5-8 ℃, add cyanuric chloride 50Kg to stir after 10 minutes, add the sour 70.11Kg that is situated between to finish rear pH=2.1 and transfer pH=3-5 with 10% sodium carbonate solution, under this medium, temperature 0-5 ℃ was reacted 4-5 hour, got a step condensated liquid.
B) diazotization: add end water 600Kg to add again P-aminoazobenzene-4-sulfonic acid 80.11Kg in pot, be warming up to 55-65 ℃, adjusting pH with 30% sodium hydroxide solution is 7.5, add Sodium Nitrite 18.87Kg to mix 20 minutes even rear hours hydrochloric acid solns of using, mix trash ice and keep 15-20 ℃ of kettle temperature, keep Sodium Nitrite excessive, be that potassium iodide starch paper is blueness, it is blue that congo-red test paper is, and reacted with this understanding 2 hours, gets diazo liquid.Wherein the preparation of hydrochloric acid soln is to add end water 100Kg in pot, then adds hydrochloric acid 79.2Kg, then adds trash ice 100Kg.
C) coupling: diazo liquid is added in primary condensation liquid, and lower than 15 ℃, finishing rear use 10% sodium carbonate solution accent pH is 6-7, reacts with this understanding 3 hours until diazo liquid disappears, and gets coupling solution with trash ice insulation degree.
D) two the step condensations: in one barrel with amino dodecane 48.9Kg, after adding N methyl-2-pyrrolidone 20.79Kg to stir all after ethanol 30.2Kg dissolving, add coupling solution, stir after 5 minutes with 60-65 ℃ of chuck intensification, and be 7.5-8 with 10% sodium carbonate adjustment pH simultaneously, reacted with this understanding 8 hours, and got two step condensated liquids.
K) finished products: two step condensated liquids are adjusted to required product intensity with Sodium sulfate anhydrous.min(99), and then spraying drying directly is packaged to be finished product.
Implement 4
A) a step condensation: add end water 100Kg in pot, add trash ice 300Kg, temperature 8-10 ℃, add cyanuric chloride 50Kg to stir after 10 minutes, add the sour 70.11Kg that is situated between, finish rear pH=2.1, transferring pH with 10% sodium carbonate solution is 3-5, and under this medium, temperature 0-5 ℃ was reacted 5 hours.
B) diazotization: add end water 600Kg to add P-aminoazobenzene-4-sulfonic acid 80.11Kg in pot again, be warming up to 55-65 ℃, adjusting pH with 30% sodium hydroxide solution is 7.5, adds Sodium Nitrite 18.87Kg to mix 20 minutes evenly rear standby.
C) another the pot in add end water 100Kg to add hydrochloric acid 79.2Kg to add again trash ice 100Kg after, above-mentioned mixed solution is added mentioned solution with about 2-3 hour, keep 15-20 ℃ of kettle temperature with trash ice simultaneously, finish and keep Sodium Nitrite excessive, be that potassium iodide starch paper is blueness, it is blue that congo-red test paper is, and reacted with this understanding 2 hours.
D) coupling: diazo liquid is added in primary condensation liquid, and lower than 15 ℃, finishing rear use 10% sodium carbonate solution accent pH is 6-7, reacts with this understanding 3 hours until diazo liquid disappears, and gets coupling solution with trash ice insulation degree.
E) two the step condensations: in one barrel with amino dodecane 48.9Kg, after adding N methyl-2-pyrrolidone 20.79Kg to stir all after ethanol 30.2Kg dissolving, add coupling solution, stir after 5 minutes with 55-60 ℃ of chuck intensification, and be 8-8.5 with 10% sodium carbonate adjustment pH simultaneously, reacted with this understanding 6 hours.
L) finished products: two step condensated liquids are adjusted to required product intensity with Sodium sulfate anhydrous.min(99), and then spraying drying directly is packaged to be finished product.
The product of above-described embodiment 1-4 preparation must be measured with intensity as follows:
| Lot number | Must measure | Intensity | Folding hundred must be measured |
| 1 | 300 | 110 | 330.00 |
| 2 | 292 | 112 | 327.04 |
| 3 | 296 | 110 | 325.60 |
| 4 | 306 | 106 | 324.36 |
| On average | 298.5 | 109.5 | 326.75 |
By the mean value calculation to the prepared using amount of above-described embodiment 1-4, and and the materials amount of the technical scheme of background technology part relatively, the comparison that draws the amount of composition used under identical output, as follows:
Improved yield by process modification, eliminated processing wastewater, economic benefit and social benefit are obvious.the present invention discloses and has proposed to utilize the synthetic method of phase-transfer catalyst production acid red R 3 G and changed the processing condition of two step condensations, those skilled in the art can suitably improve the raw material process parameter by using for reference this paper content, the links such as processing step realize, method of the present invention and technology are described by preferred embodiments, person skilled obviously can be within not breaking away from content spirit and scope of the present invention to method of the present invention and technology is changed or suitably change realize the technology of the present invention with combination, special needs to be pointed out is the replacement that all are similar and change apparent to those skilled in the art, they are deemed to be included in the present invention's spirit scope and content.
Claims (2)
1. method of utilizing phase-transfer catalyst to produce acid red R 3 G, the method comprises a step condensation, diazotization, coupling, two step condensation and finished products steps, it is characterized in that in two step condensation courses, amino dodecane being added the N-Methyl pyrrolidone phase-transfer catalyst after with dissolve with ethanol, in two step condensations, temperature of reaction is 50-65 ℃, and pH is 7.0-10.5.
2. method according to claim 1, is characterized in that the method comprises the steps:
A) a step condensation: add in frozen water cyanuric chloride in 0-10 ℃ stir 10 minutes after, slowly add the acid that is situated between, finishing rear use 10% sodium carbonate solution, to transfer pH be 3.0-6.5, reacted with this understanding 4-5 hour to get a step condensated liquid;
B) diazotization: add P-aminoazobenzene-4-sulfonic acid in water, be warming up to 55-65 ℃, adjusting pH with 30% sodium hydroxide solution is 7.5-8.5, all add Sodium Nitrite to mix after dissolving, then above-mentioned mixed solution was added the aqueous hydrochloric acid for preparing in 2-3 hour, keeping temperature is 10-20 ℃, guarantee that wherein Sodium Nitrite is excessive, be that potassium iodide starch paper is blueness, it is blue that congo-red test paper is, and reacted with this understanding 1-2 hour to get diazo liquid;
C) coupling: diazo liquid is added in primary condensation liquid, and transferring pH with 10% sodium carbonate solution is 6-7, and guarantees temperature lower than 15 ℃ with frozen water, and reacts with this understanding 2-3 hour, gets coupling solution;
D) two the step condensations: with amino dodecane with dissolve with ethanol after, add the N-Methyl pyrrolidone phase-transfer catalyst to mix, then add above-mentioned coupling solution, chuck is risen to 50-65 ℃ after stirring, and be 7.0-10.5 with 10% sodium carbonate solution accent pH, reacted with this understanding 5-8 hour to get two step condensated liquids;
Finished products: two step condensated liquids are adjusted to required product intensity with Sodium sulfate anhydrous.min(99), and then spraying drying directly is packaged to be finished product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200810154110 CN101585973B (en) | 2008-12-12 | 2008-12-12 | Method for synthesizing acid red R3G by utilizing phase transfer catalysts |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200810154110 CN101585973B (en) | 2008-12-12 | 2008-12-12 | Method for synthesizing acid red R3G by utilizing phase transfer catalysts |
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| CN101585973A CN101585973A (en) | 2009-11-25 |
| CN101585973B true CN101585973B (en) | 2013-05-08 |
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| CN112210228B (en) * | 2020-10-23 | 2023-01-24 | 浙江亿得新材料股份有限公司 | Preparation process of high-fastness and high-solubility red dye |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CH682667A5 (en) * | 1991-03-30 | 1993-10-29 | Sandoz Ag | Anionic disazo. |
| DE4408197A1 (en) * | 1994-03-11 | 1995-09-14 | Basf Ag | Reactive disazo dyes with two anchors based on cyanuric chloride |
| CN1687240A (en) * | 2005-04-21 | 2005-10-26 | 赵卫国 | SGL-BR of blue active azo dye and preparation thereof |
| CN101125964A (en) * | 2007-08-14 | 2008-02-20 | 天津市德凯化工有限公司 | Synthesis method for acid red R3G adapted for virgin pulp spray |
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Granted publication date: 20130508 Termination date: 20161212 |