JPH03131617A - Condensate of carbazolesulfonic acid or its salt and formaldehyde and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject condensate useful as a surfactant and a dispersing agent by sulfonating carbazole with (fuming) sulfuric acid and then condensing with formaldehyde. CONSTITUTION:The objective condensate is expressed by formula I [x and y are 0-2; x+y is 1-4; n is 2-100; M is H, ammonium, alkali metal, alkaline-earth metal or amine]. The condensate of formula II can be produced by sulfonating carbazole with (fuming) sulfuric acid and then condensing with formaldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a carbazole sulfonic acid or its salt-formaldehyde condensate and a method for producing the same.

(Prior Art) To the best of our knowledge, carbazole sulfonic acid or its salt-formaldehyde condensate and its production method have not been reported so far. The method for producing carbazole sulfonic acid is described in West German Patent No. 603945 and West German Patent No. 268787;
There is no mention of the method.

(Problems to be Solved by the Invention) As a result of intensive research in view of the current state of technology, the present inventors have discovered a new carbazole by adding formaldehyde to carbazole sulfonic acid, causing a condensation reaction, and neutralizing if necessary. They discovered that a sulfonic acid or its salt-formaldehyde condensate can be obtained, and completed the present invention.

(Means for Solving the Problem) The problem is solved by the following general formula (I) (wherein, X is 0 or an integer of 1 to 2, y is 0 or an integer of 1 to 2, and x y is an integer from 1 to 4, n is a number from 2 to 100, and M is hydrogen, ammonium, an alkali metal, an alkaline earth metal, or an amine. - achieved by formaldehyde condensates.

Moreover, the above-mentioned problem is solved by the general formula (II) (So 3 H
) x (80311) y (where x, y and n are the same as above).

Furthermore, the above-mentioned problem is solved by the general formula (m) (wherein xSy and n
is as described above, and M' is ammonium, an alkali metal, an alkaline earth metal, or an amine. )
This can also be achieved by a method for producing a carbazole sulfonate-formaldehyde condensate represented by:

(Function) As the carbazole sulfonic acid used in the present invention, carbazole sulfonated by a known method can be used. Examples include carbazole-monosulfonic acid, carbazole-disulfonic acid, carbazole trisulfonic acid, or a mixture thereof, which is usually obtained by sulfonation using concentrated sulfuric acid, or carbazole-tetrasulfonic acid, which is obtained by sulfonation with fuming sulfuric acid. .

The carbazole to be subjected to sulfonation used in the present invention is not particularly limited, but includes carbazole having a purity of 96% by market weight or higher and commonly used for industrial purposes.

A carbazole sulfonic acid-formaldehyde condensate represented by general formula (II) H (where x, y and n are the same as above) can be obtained by condensing carbazole sulfonic acid and formaldehyde. can.

The formaldehyde used in the present invention is not particularly limited as long as it is formaldehyde or a solution containing formaldehyde, but a 35% formalin solution is usually used. The reaction between 35% formalin solution and carbazole sulfonic acid is an isostatic reaction.

The condensation reaction is generally carried out at 60-100°C, preferably at 70-100°C.
It is carried out with stirring at a temperature of 90° C. for 2 to 10 hours, preferably 4 to 6 hours.

Further, the condensation of carbazole sulfonic acid and formalin can be carried out as it is without separating and purifying the sulfonic acid which has been raised in the presence of excess concentrated sulfuric acid used in the sulfonation. For example, when carbazole is sulfonated with concentrated sulfuric acid, the amount of concentrated sulfuric acid used is 10% of carbazole.
200 to 30 parts by weight (hereinafter simply referred to as parts)
0 parts, concentrated sulfuric acid is charged to the reactor, and carbazole is gradually added. The sulfonation is carried out at a temperature of 60-100°C, preferably 70-90°C, for 2-10 hours, preferably 4-6 hours. After the sulfonation reaction, the reaction mixture is diluted by adding 100 to 200 parts of water.

To this, 10 to 70 parts of a 35% formalin solution, preferably 35 to 55 parts, was added dropwise over 1 to 3 hours.
The condensation reaction is carried out at a temperature of 0°C, preferably 70 to 90°C, for 2 to 10 hours, preferably 4 to 6 hours. After the completion of the condensation reaction, a hydroxide such as calcium hydroxide Ca (OH2) is added to precipitate excess sulfuric acid as calcium sulfate CaSO4 and filtered out to obtain a carbazole sulfonic acid-formaldehyde condensate represented by formula H. It will be done.

When the carbazole sulfonic acid-formaldehyde condensate represented by the general formula (1) thus obtained is neutralized by adding alkali metals, alkali-1-class metals, ammonia, amines, etc., the carbazole represented by the formula (2) is neutralized. A sulfonate-formaldehyde condensate is obtained.

The alkali metals used in the present invention include lithium,
Examples of alkaline earth metals include magnesium, calcium, strontium, barium, etc., preferably calcium or magnesium. Amin, 2nd
Examples include amines or tertiary amines. Examples of amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, tonoethylamine, n-propylamine, isopropylamine,
Examples include alkylamines such as diisopropylamine, n-butylamines and isobutylamines, alkyleneamines such as ethylenediamine and diethylenetriamine, and 7t'h group amines such as pyridine and aniline. The thus obtained carbazole-formaldehyde condensates represented by formulas (I) and (II) are used as high-performance surfactants and dispersants. especially,
In order to use the carbazole sulfonic acid or its salt-formaldehyde condensate as a surfactant or dispersant, its effectiveness can be enhanced by specifying its molecular weight. That is, in the condensation reaction, the amount of formaldehyde added is 0.5 to 1.5 mol, preferably 0.7 to 1.1 mol, per 1 mol of carbazole sulfonic acid. If the amount of formaldehyde added is less than 0.5 mol, the degree of polymerization of the resulting condensate will be low, and the ``-1 s average fraction amount will be less than 1,000.

Molecular weight less than 1,000? This condensate has poor performance as a dispersant and is therefore undesirable. On the other hand, when the amount of formaldehyde added is more than 1.5 moles, the degree of polymerization of the resulting condensate is high, and the average molecular weight is 15.000 or more. A condensate having a molecular weight of 15,000 or more is insoluble in water and cannot be used as an aqueous solution, and is not preferred as a dispersant. Therefore, the weight average molecular weight of the carbazole-form t, aldehyde condensate is 1000 to 15,000,
In particular, it is preferably in the range of 2°000 to 10,000.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

In addition, in the examples, the weight average molecular weight of the condensate is determined by the gel permeation chromatography column TSKge.
1-G3000SWXL19 and TSKgel-G2
The results of measurements using gel permeation chromatography (GPC) combined with 000SWXL (manufactured by Tosoh Corporation) were analyzed using several types of sodium polystyrene sulfonate (with known weight average molecular weights) with different f distributions. This is a conversion based on a calibration curve created as a mulberry substance.

Example 1 240 parts of concentrated sulfuric acid with a concentration of 98% by weight was placed in a 19-eye round bottom flask equipped with a thermometer, a condenser, and a stirrer, and while stirring, 100 parts of 97% by weight carbazole was added and heated to 80°C. The mixture was dissolved at elevated temperature, and a sulfonation reaction was carried out at this temperature for 5 hours to obtain carbazole sulfonic acid. This reaction solution was diluted by adding 100 parts of water, the temperature was adjusted to 80°C, and 34.6 parts of a 35% formalin solution was added dropwise over 3 hours. After the dropwise addition, a line combination reaction was carried out at a temperature of 80° C. for 5 hours. The obtained reaction product was diluted by adding 300 parts of water, cooled, and desulfurized by adding calcium hydroxide. After filtration, the filtrate was neutralized by adding sodium hydroxide to form a carbazole sodium sulfonate formalin condensate. 695 parts of an aqueous solution were obtained. When the average molecular weight of this product was measured by weight - 1, MW = 26
I got a result of 00.

Moreover, the infrared absorption spectrum of this condensate was as shown in the drawing.

Examples 2 to 5 In Example 1, sulfonation was carried out under the same conditions as in Example 1, and 44.6 parts of 35% formalin solution,
Added 4 parts of 54°, 54.4 parts, and 6 parts of 34°, condensation temperature 80°C, 80°C, 95°C, 95°C, condensation time 5 hours, 5
The condensation reaction was carried out in the same manner as in Example 1 except for the following times: 2 hours, 2 hours. The results are shown in Table 1.

Comparative Examples 1 and 2 In Example 1, sulfonation was carried out under the same conditions as in Example 1, and 19.8 parts of a 35% formalin solution was added,
The condensation reaction was carried out in the same manner as in Example 1 except that 74.3 parts were added. The results are shown in Table 1.

Reference example 1 (Mortar flow test) (i) Blend amount Water 286g Ordinary Portland cement 520gf-1-shi
Toyoura standard sand 1,040g (if) kneaded. Using a mortar mixer with a paddle as specified in JIS R5201, add cement and sand and dry mix at low speed for 30 seconds. Add 286g of water containing a dispersant and mix at high speed for 3 minutes. Ta.

(iii) Measurement of mortar flow value Flow table specified in JIS R5201 - [
-The flow cone is removed seven times and vibrated 1.5 times at a rate of 1 time/1 second.The diameter of the spread of the mortar is defined as the mortar flow (direction).The results are shown in Table 2. .

The amount of the water-soluble condensate added was 0.25 iTi:% by weight based on the cement in terms of solid content.

5 (Table 3 (Effects of the Invention)) The present invention is a novel nacarbazole-formaldehyde condensate represented by -layer structure (1) and (2), which has improved performance as a surfactant and dispersant and is extremely useful for white applications. It is.

Furthermore, according to the production method of the present invention, the carbazole-form aldehyde condensate can be provided in one go very easily.

In particular, regarding the performance as a dispersant, various fi'' mechanized gold compounds (for example, dyes, pigments, agricultural products, etc.) and solids (coal, cement), etc. have excellent performance as a dispersant, and can be used alone or in a variety of ponds. Can be used in combination with surfactants.

[Brief explanation of the drawing]

The drawing is Carbazole sulfonic acid according to the invention salt-formaldehy Infrared absorption spectra of hydrogen-based condensates nine This is a torque diagram.

Claims (1)

[Claims] 1. The following general formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, x is 0 or an integer of 1 to 2, and y is 0 or 1 to 2, x+y is an integer from 1 to 4, n is a number from 2 to 100, and M is hydrogen, ammonium, an alkali metal, an alkaline earth metal or an amine). Sulfonic acid or its salt-formaldehyde condensate. 2. General formula (II) characterized by sulfonating carbazole with sulfuric acid or fuming sulfuric acid and then condensing it with formaldehyde ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (However, in the formula, x, y and n are the same as above.) A method for producing a carbazole sulfonic acid-formaldehyde condensate. 3. General formula (characterized by sulfonating carbazole with sulfuric acid or fuming sulfuric acid, then condensing the sulfonated product with formaldehyde, and further neutralizing the condensate)
III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (However, in the formula, x, y, and n are the same as above, and M^- is ammonium, alkali metal, alkaline earth metal, or A method for producing a carbazole sulfonate-formaldehyde condensate represented by: