JPH0621141B2 - Method for producing phenanthrene 9-sulfonate formalin condensate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] In the present invention, phenanthrene is subjected to sulfonation using concentrated sulfuric acid to selectively produce phenanthrene 9-sulfonic acid, and formalin is further added to the phenanthrene. The present invention relates to a method for producing a phenanthrene 9-sulfonate formalin condensate by performing a condensation reaction.

As phenanthrene generally used for sulfonation,
Besides normal phenanthrene, industrial crude phenanthrene is used. This product is obtained, for example, by distilling the bottom residue from which anthracene and carbazole are separated from a cake that crystallizes by cooling anthracene oil, but it is still a substance that is not used.

The present inventors have made extensive studies on this effective use. As a result, phenanthrene 9-sulfonic acid is selectively produced by sulfonation of phenanthrene and further condensed with formalin to obtain a phenanthrene 9-sulfonate formalin condensate. Found that they have characteristics as a high-performance surfactant and a dispersant, and arrived at the present invention.

[Prior Art] In the present invention, phenanthrene is used with concentrated sulfuric acid,
This is a method for producing phenanthrene 9-sulfonic acid by sulfonation and then performing a condensation reaction with formalin to produce the condensate. As a method for producing phenanthrene monosulfonic acid, 1. L. F. Fieser. Organic Synt
ses. 16.63. (1936) 2. L. F. Fieser. J. Am. Chcm. So
c. 51.2460. (1929) 3. Sisten. Mariam. Grace Sol
omon. J. Org. Chcm. 22.1649 (1
957), but all of them are methods for obtaining a phenanthrene monosulfonic acid mixture, and no method for selectively producing phenanthrene 9-sulfonic acid has been reported so far. Further, a method for producing a phenanthrene 9-sulfonic acid formalin condensate obtained by condensing phenanthrene 9-sulfonic acid and formalin has not been reported so far.

[Problems to be Solved by the Invention] As a result of intensive studies in view of the current state of the art, the present inventors have conducted sulfonation of phenanthrene with concentrated sulfuric acid to obtain phenanthrene 9-sulfonic acid. The present invention has been reached in which a phenanthrene 9-sulfonic acid formalin condensate is produced by performing a condensation reaction by selectively producing and further adding formalin.

[Means for Solving the Problems] In the present invention, when phenanthrene is sulfonated using concentrated sulfuric acid, the amount of concentrated sulfuric acid used is phenanthrene 10
60 parts by weight to 200 parts by weight with respect to 0 parts by weight, sulfonation is performed at a reaction temperature of 70 ° C. to 100 ° C., and formalin is further added to phenanthrene 9-sulfonic acid 100 parts by weight.
35 parts by weight to formalin 25 parts by weight to 45 parts by weight
The present invention relates to a method for producing a phenanthrene 9-sulfonate formalin condensate, which comprises adding formalin in the range of parts by weight to carry out the condensation reaction at a condensation reaction temperature of 80 ° C to 100 ° C.

The method for selectively producing phenanthrene 9-sulfonic acid according to the present invention will be described in more detail. When phenanthrene is sulfonated with concentrated sulfuric acid, the sulfonation reaction temperature is 70 ° C to 100 ° C. Preferably, 75 ° C ~
It is 85 ° C. When the reaction temperature is 70 ° C. or lower, phenanthrene 9-sulfonic acid can be selectively produced, but the sulfonation reaction rate is slow, and it takes a long time to complete the sulfonation, and it takes a predetermined time. If sulfonation is carried out, unreacted phenanthrene will be mixed, and separation and purification thereof will be extremely difficult and not economically effective.

If the reaction temperature is 100 ° C. or higher, the sulfonation reaction rate increases, but the obtained phenanthrene 9-sulfonic acid is not stable against temperature and exhibits a rearrangement reaction.
It becomes phenanthrene 2-sulfonic acid and 3-sulfonic acid, and furthermore, phenanthrene disulfonic acid is produced, and phenanthrene 9-sulfonic acid cannot be selectively obtained. In addition, concentrated sulphonic acid is used for the sulfonation, but the amount used is phenanthrene 10
It is 60 to 200 parts by weight with respect to 0 parts by weight. It is preferably 100 to 150 parts by weight.

If the amount of concentrated sulfuric acid used is 60 parts by weight or less, the viscosity in the reaction system increases during sulfonation, making it difficult to continue stirring, and the reaction becomes non-uniform. When the amount used is in the range of 200 parts by weight or more, the viscosity in the reaction system decreases and the stirring becomes good, but the ratio of concentrated sulfuric acid to phenanthrene increases, and phenanthrene 9-sulfonic acid cannot be selectively obtained. Then, phenanthrene 2-sulfonic acid and phenanthrene 3-sulfonic acid are produced, and further phenanthrene disulfonic acids are produced.

It was also found that when fuming sulfuric acid was used in the sulfonation of phenanthrene, phenanthrene became phenanthrene disulfonic acid, and phenanthrene 9-sulfonic acid could not be selectively produced.

In the present invention, generally, phenanthrene 9-sulfonic acid is subjected to sulfonation with concentrated sulfuric acid to selectively produce phenanthrene 9-sulfonic acid, and the obtained sulfonic acid is not separated and purified, and a reaction liquid of phenanthrene 9-sulfonic acid is obtained. Use
Formalin is added to this to carry out a condensation reaction to produce the condensate. Of course, even if phenanthrene 9-sulfonic acid is separated and purified from the reaction solution, and formalin is added to this, the condensation reaction is performed. I don't care. For the method for producing a phenanthrene sulfonic acid condensate,
Up to now, the possibility of use as a dispersant has been reported in Japanese Patent Application Laid-Open No. 54-71112, but no production method thereof has been reported. The present inventors, without separating and purifying the phenanthrene 9-sulfonic acid obtained by the sulfonation, in the sulfonation reaction solution, 35 parts by weight of formalin 35 wt% to 25 parts by weight to 45 parts by weight of sulfonic acid. 80 parts
They have found that a condensation reaction is carried out at a temperature of 100 ° C. to obtain an aqueous solution of the sulfonic acid formalin condensate.

In the formalin condensation reaction, the added amount of 35% formalin is 25 parts by weight to 45 parts by weight with respect to 100 parts by weight of phenanthrene 9-sulfonic acid, but preferably,
35 to 40 parts by weight.

When the amount of formalin added is small (for example, the formalin / phenanthrene sulfonic acid molar ratio is 0.7 or less)
Has a low degree of polymerization and an average molecular weight of 4
It becomes not more than 00, and the obtained condensate is not preferable because the performance as a dispersant is deteriorated. Further, when the amount of formalin added is large (for example, the molar ratio of formalin / phenanthrenesulfonic acid is 1.2 or more), the degree of polymerization of the obtained condensate is large, the average molecular weight is 3000 or more, and the compound becomes insoluble in water. It cannot be obtained as a formalin condensate aqueous solution, and therefore cannot be used as a dispersant.

The average molecular weight of the phenanthrene 9-sulfonic acid formalin condensate is preferably 400 to 2000, and most preferably 500 to 1500. An example of producing an aqueous solution of a phenanthrene 9-sodium sulfonate formalin condensate having a performance suitable as a dispersant will be shown below, but the present invention is not limited to this.

98% concentrated sulfuric acid for 1 part by weight of phenanthrene, 1
Sulfone conversion is carried out using 15 parts by weight, and 100 parts by weight of water is added to dilute the obtained sulfonic acid reaction solution. This solution is adjusted to 80 ° C to 85 ° C, and 40 parts by weight of a 35% formalin solution is added dropwise over 1 hour.

After the dropping, the condensation reaction is performed at 95 ° C. for 8 hours. Add 100 parts by weight of calcium carbonate to the product after the condensation reaction,
Residual sulfuric acid is converted to calcium sulfate and removed by filtration. Furthermore, 35 parts by weight of sodium carbonate was added to the filtrate,
The precipitated insoluble calcium carbonate is removed by filtration to obtain an aqueous solution of phenanthrene 9-sodium sulfonate formalin condensate. Then, the product is obtained by adjusting the concentration of this aqueous solution.Of course, when sodium sulfate is allowed to be mixed in the product, caustic soda is added to the reaction liquid that has undergone the condensation reaction to neutralize and adjust the concentration. The product of phenanthrene 9-sulfonate sodium formalin condensate may be obtained.

[Effect of the Invention] In the present invention, when phenanthrene 9-sulfonic acid is produced from phenanthrene and concentrated sulfuric acid, 60 parts by weight to 200 parts by weight of concentrated sulfuric acid is used with respect to 100 parts by weight of phenanthrene, and the temperature is 70%. This is a method for producing a phenanthrene 9-sulfonate formalin condensate obtained by obtaining phenanthrene 9-sulfonic acid with a high selectivity by sulfonation in the range of 100 ° C to 100 ° C and further condensing it with formalin. Is useful as a surfactant and a dispersant because it exhibits its performance.

Especially, in terms of performance as a dispersant, various organic compounds (eg dyes, pigments, agricultural chemicals, etc.) and solids (coal, cement)
It has excellent properties as a dispersant and is used alone or in combination with various other surfactants.

[Examples] Next, the present invention will be described more specifically with reference to Examples for the production of a phenanthrene 9-sulfonate formalin condensate.

Example 1 110 parts by weight of 98% by weight concentrated sulfuric acid was placed in a 300 ml four-neck round bottom flask equipped with a thermometer, a condenser and a stirrer, and 100 parts by weight of 93% by weight industrial phenanthrene was added thereto while stirring. In addition, it heated up at 80 degreeC and melted. The sulfonation reaction was carried out at this temperature for 8 hours to obtain 210 parts by weight of a reaction liquid.

When the product in this reaction solution was analyzed by liquid chromatography, phenanthrene 9-sulfonic acid was 79% by weight, phenanthrene 1-sulfonic acid was 11% by weight, and phenanthrene 2- Sulfonic acid is 3% by weight, and phenanthrene 3-sulfonic acid is 3% by weight.
% By weight, and in addition, 4% by weight of phenanthrene sulfonic acids was obtained. 100 parts by weight of water was added to this reaction solution to dilute it, the temperature was adjusted to 80 ° C., and 38.8 parts by weight of a 35% formalin solution was added dropwise over 1 hour. After the dropping, the condensation reaction was performed at a temperature of 95 ° C. for 8 hours. Then, remove the reaction mixture into a 1000 ml beaker and add 300 ml of water.
9 parts by weight of calcium carbonate
3.6 parts by weight was added, and the precipitated calcium sulfate was removed by filtration. While stirring, 33 parts by weight of sodium carbonate was added to the filtrate, and the precipitated insoluble calcium carbonate was removed by filtration. The filtrate was concentrated to adjust the concentration to obtain 412 parts by weight of 48% phenanthrene 9-sodium sulfonate formalin condensate.
The average molecular weight of this product was determined by gel chromatography (ALC / GPC 24 manufactured by Japan Waters Limited).
4, column packing material: measured with Protin Pack I 60 × 2), and a result of M = 800 was obtained.

Examples 2 to 4 In Example 1, 98 parts by weight of phenanthrene is 98 parts by weight.
% Concentrated sulfuric acid (110 parts by weight) was added, and the sulfonation reaction temperatures were 70 ° C., 90 ° C. and 100 ° C., and the reaction time was 12
For 7 hours, 8 hours and 7 hours, 37% by weight, 40 parts by weight and 35 parts by weight of 35% formalin are added, and the condensation temperature is 95 ° C, 95 ° C, 90 ° C, reaction time, 7. The sulfonation and condensation reactions were carried out in the same manner as in Example 1 except for 5 hours, 12 hours and 8 hours. The results are shown in Table-1.

Comparative Examples 1 to 2 In Example 1, sulfonation was performed under the same conditions as in Example 1, and 15% by weight and 50 parts by weight of 35% formalin were added, respectively, and the reaction temperature was 95 ° C. and the reaction time was 8 hours. The condensation reaction was performed in the same manner as in 1. The results are shown in Table-2.

Examples 5 to 7 In Example 1, 100 parts by weight of phenanthrene is 98 parts by weight.
% Concentrated sulfuric acid 110 parts by weight, 150 parts by weight, and 200 parts by weight were charged, the reaction time was 12 hours, 8 hours, and 7 hours, and the sulfonation was performed in the same manner as in Example 1 except for the reaction temperature and the like. 35% formalin was added to 40 parts by weight, 38 parts by weight, 36 parts by weight and the condensation temperature was 95 ° C.
90 ° C, 80 ° C, reaction time 8 hours, 7.5 hours, 7.5
The condensation reaction was performed in the same manner as in Example 1 except for time. The results are shown in Table-1.

Comparative Examples 3 to 4 In Example 1, sulfonation was performed under the same conditions as in Example 1, 40% by weight of 35% formalin was added, and reaction time was 70 ° C. and 120 ° C. was 12 hours.
The condensation reaction was carried out in the same manner as in Example 1 for 8 hours.
The results are shown in Table-2.

Claims (2)

[Claims] 1. When phenanthrene is sulfonated using concentrated sulfuric acid, the amount of concentrated sulfuric acid used is 60 parts by weight to 200 parts by weight, based on 100 parts by weight of phenanthrene, and sulfonated. The reaction temperature 70 ° C to 100 ° C
Further, formalin is added in the range of 25 to 45 parts by weight of 35% by weight formalin to 100 parts by weight of phenanthrene 9-sulfonic acid, and the condensation reaction temperature is condensed in the range of 80 to 100 ° C. A method for producing a phenanthrene 9-sulfonate formalin condensate, which comprises carrying out a reaction. 2. The method according to claim 1, wherein the phenanthrene 9-sulfonate formalin condensate has an average molecular weight of 400 to 2000.