CN101434565A

CN101434565A - Method for synthesizing chrome azurol S

Info

Publication number: CN101434565A
Application number: CNA2007101704562A
Authority: CN
Inventors: 顾震虎; 戴林荣
Original assignee: SHANGHAI SAN'AISI REAGENT CO Ltd
Current assignee: SHANGHAI SAN'AISI REAGENT CO Ltd
Priority date: 2007-11-15
Filing date: 2007-11-15
Publication date: 2009-05-20

Abstract

A sulfonation reaction is carried out between fuming sulfuric acid with a sulfur trioxide content of 20 percent to 30 percent (weight) and an acid chrome pure blue B, and the mass ratio of the fuming sulfuric acid and the acid chrome pure blue B is 1-1.2:0.1 and sulfonation temperature is 80 DEG C to 90 DEG C. Heat preservation is carried out at 100 DEG C to 105 DEGC for 1 hour to 2 hours, and then settling is carried out by the use of 15 percent to 25 percent (weight) of salt water. Weight ratio of sulfonated products and the salt water is equal to 1:3 to 1:5. And then absolute ethyl alcohol is adopted for extraction and filtrate is condensed under the reduced pressure of less than or equal to 92kPa. The pure sulfonated products and a sodium hydroxide aqueous solution are subjected to neutralization reaction for salifying, and then are filtered, condensed under the reduced pressure and dried to obtain a chromazurine S product with the yield of 67 percent to 75 percent, the purity of 70 percent to 80 percent and the pH value of 5 to 6.5.

Description

A kind of synthetic method of chrome azurol S

One, technical field

The present invention relates to the synthesis technique of chrome azurol S, relate to 3 " sulfo groups-2 " or rather, 6 " two chloro-3,3 '-dimethyl-4-hydroxyl fuchsone-5,5 '-synthetic method of dicarboxylic acid sodium salt.

Two, background technology

Chrome azurol S has another name called 3 " sulfo groups-2 ", 6 " two chloro-3,3 '-dimethyl-4-hydroxyl fuchsone-5,5 '-the dicarboxylic acid trisodium salt;

Another name: mordant dyeing indigo plant 13; Mordant dyeing indigo plant 29.

Chemical structural formula is:

Outward appearance is the reddish-brown powder, is brown yellow solution after water-soluble, is slightly soluble in water, and the aqueous solution is reddish-brown, and maximum absorption wavelength 458nm has pungency.Can be used as indicator, chelometric titration aluminium, calcium, iron, nickel and thorium.At spectrophotometric analysis colorimetric estimation aluminium, cerium, cobalt, chromium, copper, iron, gallium, hafnium, indium, lanthanum, manganese, molybdenum, nickel, palladium, rhodium, scandium, thorium, titanium, vanadium, yttrium, shovel, zirconium plasma and amide.Make the tinting material of fiber, plastics, coating and tackiness agent.So this chrome azurol S is a kind of important organic compound, broad-spectrum staining agent.

Preparation as for chrome azurol S, generally by 2,6-dichlorobenzaldehyde and ortho-cresotic acid are condensed into shadow in the vitriol oil, 60～70 ℃ of Sodium Nitrite oxidations that are used in the vitriol oil of what then, oxidizing reaction finishes, and resultant is toppled in the entry, after filtration, washing and dry, become sodium salt with the caustic soda solution-treated again, thereby make chrome azurol S.Prior art US Pat.Ne877.054; An.31,1908 technology that disclose are exactly preparation process as the aforementioned.This prior art preparation process that only underdrawed, product quality indicator is not introduced, and the also clear problem of expressing about these aspects of invention effect all needs to be added on solution.

Present inventors are according to the local resources situation, directly float blue B by acidic intermedium and oleum carries out sulfonation reaction, and resultant changes into sodium salt again, promptly makes chrome azurol S.This method route is short, yield is high, purity is high, has significant superiority.

Reaction formula of the present invention is as follows:

Chrome azurol S

If add 1 molar sodium hydroxide, then product just only becomes sodium monosulfate salt 3.

Reaction just becomes:

Three, summary of the invention

Present inventors utilize the local acidic intermedium of producing to float blue B as initial feed in conjunction with the local raw material source, through specializing in, propose complete technical scheme.

In the technical scheme of invention, the synthesis step of chrome azurol S comprises: stir down (1), float blue B with the oleum sulfonation acidic intermedium that contains 20～30% (weight) sulphur trioxide, the weight ratio that oleum and acidic intermedium float blue B is 1～1.2:0.1, the sulfonation reaction temperature is 80～90 ℃, and what reacted 1～2 hour for 100～105 ℃.(2) with 15～25% (weight) salt water washing sulfonated products, filtration, the dry sulfonated product that gets, sulfonated products and brinish weight ratio are 1:3～5.(3) extract sulfonated product with dehydrated alcohol, the weight ratio of sulfonated product and dehydrated alcohol is 1:10～13, the 24 hours after-filtration that reflux, and concentrating under reduced pressure obtains pure sulfonated product.(4) carry out neutralization reaction with aqueous sodium hydroxide solution and pure sulfonated product and generate single sodium or double sodium salt or trisodium salt, sulfonated product: pure water: the weight ratio of sodium hydroxide is 1:7.5～8.0:0.05～0.08, product behind the salify after filtration, concentrating under reduced pressure, dry product chrome azurol S, yield 67～75%, purity 70～80%, outward appearance: dark-brown～black crystalline powder, the pH value equals 5～6.5.

The used oleum of the present invention is better with the oleum that contains 20%～23% sulphur trioxide.

Better with 15～20% (weight) salt water washing sulfonated product, drying temperature is 70～75 ℃.

Vacuum tightness≤the 92Kpa of concentrating under reduced pressure sulfonated product.

The pH value of solution value that neutralization reaction generates behind the sodium salt equals 5～6.5.

According to the chrome azurol S of the invention process preparation, its cost is low, purity is high, synthetic route is short and convenient, and operation is relatively easy.The specific performance index is: yield 67～75%, purity 70～80%, outward appearance are dark-brown～black crystalline powder, pH value (in the water)=5～6.5, maximum absorption wavelength 428nm～432nm in the water, dry molecular extinction coefficient 〉=11000, vitriol≤44%, 105 ℃ weight loss on drying≤3.8%.

Four, specific implementation method

Especially exemplified by example it is described in order to implement the present invention better, but is not restriction invention.

Embodiment 1:

(1), oleum and acidic intermedium float the sulfonation reaction of blue B:

To being equipped with agitator, thermometer, charging opening, and add the oleum that 1000g contains 20～30% (weight) sulphur trioxide in the 2000mL four-hole round-bottomed flask of condenser, start stirring, add the 100g acidic intermedium gradually and float blue B, temperature of reaction is controlled at 85 ℃, after material adds, continue to stir 1 hour, be incubated to sulfonation reaction and finish (promptly 2 drip solution takes on a red color till) in 103 ℃.Stirring is cooled to 50 ℃ of blowings, reaction solution is poured in the 10L plastic tank that fills 2.5 kilograms of ice cubes, add 20% (weight) 6kg salt solution, stirring is saltoutd, and produces the red-purple throw out, after leaving standstill 2 hours, filter,, filter with 1 kilogram of salt water washing of 20% (weight) 2 times, in 75 ℃ of dryings, obtain sulfonated products 110g.

(2), extract sulfonated product with dehydrated alcohol:

Sulfonated products and 1200g dehydrated alcohol refluxed 24 hours, filtered, and were decompressed to that evaporation concentration, drying obtain the 80g sulfonated product under the 92kpa pressure.

(3) in and salify:

In the mixture of 700g deionized water and 80g sulfonated product, be added dropwise to 15% (weight) aqueous sodium hydroxide solution under stirring, regulating pH is 5～6.5, exhaust 33g15% (weight) aqueous sodium hydroxide solution, all dissolve after-filtration, filtrate is through concentrating under reduced pressure, the dry 80g chrome azurol S product that gets, yield 67%, purity 75%, outward appearance are the dark-brown crystalline powder, and the pH value equals 6～6.5 in the water, maximum absorption wavelength 428nm～432nm in the water, dry molecular extinction coefficient 〉=11000, vitriol≤44%, 105 ℃ weight loss on drying≤3.8%.

Embodiment 2:

Remove the oleum that contains 23% (weight) sulphur trioxide with 1200g, temperature of reaction is 90 ℃, in 100 ℃ of insulations 2 hours, add 15% (weight) sodium-chlor 8kg, the 1468g dehydrated alcohol, water consumption is outside the 600g in the aqueous sodium hydroxide solution and during sulfonated bodies, and other prescription is the same with embodiment 1 with operation steps.The chrome azurol S product obtains 90g as a result, yield 75%, and purity 80%, other performance index are the same with embodiment 1.

Embodiment 3:

Remove the oleum that contains 20% (weight) sulphur trioxide with 1100g, temperature of reaction is 80 ℃, and in 105 ℃ of insulations 1.5 hours, water consumption was outside the 640g in the hydro-oxidation sodium water solution and during sulfonated bodies, and other prescription and operation steps and embodiment 1 are just the same.The chrome azurol S product obtains 84g as a result, yield 70%, and purity 70%, other performance index and example 1 are just the same.

Claims

1, a kind of synthetic method of chrome azurol S is characterized in that synthesis step comprises:

(1) stirs down, float blue B with the oleum sulfonation acidic intermedium that contains 20～30 weight % sulphur trioxides, the weight ratio that oleum and acidic intermedium float blue B is 1～1.2:0.1, the sulfonation reaction temperature is 80～90 ℃, and what reacted 1～2 hour for 100～105 ℃, add 15～25 weight % salt solution in the reaction solution, stirring is saltoutd, and gets sulfonated products;

(2) with 15～25 weight % salt water washing sulfonated products, sulfonated products and brinish weight ratio are 1:3～5, filtration, the dry sulfonated product that gets;

(3) extract sulfonated product with dehydrated alcohol, the weight ratio of sulfonated product and dehydrated alcohol is 1:10～13, the 24 hours after-filtration that reflux, and concentrating under reduced pressure obtains pure sulfonated product;

(4) carry out neutralization reaction with aqueous sodium hydroxide solution and pure sulfonated product and generate single sodium or double sodium salt or trisodium salt, sulfonated product wherein: pure water: the weight ratio of sodium hydroxide is 1: 7.5～8.0:0.05～0.08, product filtration behind the salify, filtrate are through concentrating under reduced pressure, the dry product chrome azurol S that gets, yield 67～75%, purity 70～80%, pH value=5～6.5, outward appearance: dark-brown～black crystalline powder.

2, the synthetic method of chrome azurol S according to claim 1.It is characterized in that the oleum in the described step (1) is the oleum that contains 20～23 weight % sulphur trioxides.

3, the synthetic method of chrome azurol S according to claim 1 is characterized in that described step (2) is middle with 15～20 weight % salt water washing sulfonated products, and the dry drying temperature that gets sulfonated product is 70～75 ℃.

4, the synthetic method of chrome azurol S according to claim 1 is characterized in that the concentrating under reduced pressure in the described step (3) carries out under vacuum tightness≤92kpa.

5, the synthetic method of chrome azurol S according to claim 1 is characterised in that the pH value of solution value behind the neutralization reaction salify in the step (4) is 5～6.5.