JPS6055094A - Preparation of basic magnesium sulfonate - Google Patents

Abstract

PURPOSE:To prepare with a good yield and high efficiency of filtration a basic magnesium sulfonate compd. having a high Mg content and a high total basicity, by adding hydroxyacetic acid to a mixt. of an oil-soluble sulfonic acid with MgO or Mg(OH)2, etc. and passing CO2 through it. CONSTITUTION:The titled compd. is prepd. by passing CO2 through a mixt. consisting of an oil-soluble sulfonic acid (salt), MgO or Mg(OH)2 which is reactive with the acid (salt) and is used in excess of a stoichometric amt., a hydrocarbon solvent, water, a reaction promoter (e.g. ethylenediamine) and hydroxyacetic acid. In the conventional method employing alcohol or ketone in place of hydroxyacetic acid, reaction takes a long time and it is difficult to separate the product by filtration after completion of the reaction. The use of hydroxyacetic acid markedly increases filtrability and makes it easy to obtain the compd. having a high Mg content and a high total basicity with a good yield.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing basic magnesium sulfonates useful as lubricating or fuel oil additives.

The basic magnesium sulfonate as used in the present invention means a compound containing magnesium in excess of the stoichiometric amount required to neutralize the sulfonic acid.

Traditionally, a common method for making basic alkaline earth sulfonates has been to pass carbon dioxide through a mixture of an oil-soluble sulfo/acid and an alkaline earth metal oxide or hydroxide. However, in the case of basic magnesium sulfonate, compared to the case of other alkaline earth metals such as barium and calcium [7], it requires a long reaction time and it is difficult to carry out overheating after the reaction is completed. Different 0 Various methods have been proposed to overcome this problem. Typical methods include 1) passing carbon dioxide through a reaction mixture containing oil-soluble neutral magnesium sulfonate, magnesium oxide, lower alkanol, water and ethylenediamine in a petroleum medium; That is, a method in which lower alkanol, water, and ethylenediamine are included in the mixture to accelerate the reaction and improve filterability. (Refer to Japanese Patent Publication No. 49-13782) 2) A mixture containing an oil-soluble sulfonate or sulfonic acid, an excess of magnesium compound, a hydrocarbon solvent, an alcohol or ketone, water, and a reaction accelerator is subjected to oxidation under specific conditions. How to supply carbon. That is, a method in which alcohol or ketone, water, and a reaction accelerator are included to accelerate the reaction and improve the f-transactivity. (Unexamined Japanese Patent Publication No. 56-1
(See Publication No. 09821) However, these methods do not provide a sufficiently satisfactory improvement.

It is an object of the present invention to quickly separate the hydrocarbon-dissolved portion of the reaction product mixture from insoluble materials mainly from inorganic substances, to facilitate filtration, to have a rapid reaction, to have a high magnesium content, and to have a total base number. The present invention provides a method for producing highly basic magnesium sulfonate.

As a result of intensive research to achieve the above object, the present inventors found that
It has been found that the above object can be achieved by using hydroxyacetic acid instead of alcohol or ketone in conventional methods. The present invention was completed based on this knowledge.

The gist of the invention is to provide a mixture comprising an oil-soluble sulfo/acid or its salt, a substoichiometric excess of magnesium oxide or hydroxide to be reacted with, a hydrocarbon solvent, hydroxyacetic acid, water and a reaction promoter. A method for producing basic magnesium sulfonate characterized by passing carbon dioxide therethrough.

The basic magnesium sulfonate produced by the method of the present invention is an oil solution of magnesium sulfonate, which itself acts as a surfactant to disperse excess colloidal alkaline earth metal compound. It is necessary that the sulfonic acid or its salt be soluble in oil. Examples of oil-soluble sulfonic acids or salts thereof include oil-based petroleum sulfonic acids, alkylsulfonic acids, arylsulfonic acids, alkylarylsulfonic acids, and salts thereof. Magnesium salts are most preferred as salts, but other alkali and alkaline earth metals may also be used.
It may be a salt or an ammonium salt.

The amount of magnesium oxide or magnesium hydroxide used must be in excess of the stoichiometric amount for reaction with the oil-soluble sulfonic acid or its salt.

This is because this excess of these substances is dispersed and retained in the magnesium sulfonate. The preferred range is 2 to 20 equivalents relative to the equivalent of the oil-soluble sulfonic acid. Since the hydrocarbon solvent is used to maintain the mixture in a fluid state when carbon dioxide is supplied into the mixture, an amount sufficient to maintain the mixture in a fluid state is used. Examples of the hydrocarbon solvent include toluene, xylene, mineral oil, and hexane. However, it is not limited to this.

Hydroxyacetic acid has the effect of hardening and increasing the size of solid precipitates mainly composed of inorganic substances.

Therefore, the hydrocarbon dissolved portion in the reaction product and the solid precipitate can be quickly separated, and the separation is also extremely easy.

Furthermore, the magnesium content of the basic magnesium sulfonate obtained was increased to 7.5%, and the total base number (the number of KOH equivalents equivalent to sample 1 when titrated with a strong acid) was as high as 380. obtain. The amount used is preferably 0.2 to 2.5 parts by weight per 1 part by weight of magnesium oxide (5).

Water has the effect of improving the contact between the reactants and smoothing the reaction, and the amount of water used is changed depending on the amount of magnesium oxide or magnesium hydroxide used, and in the case of magnesium oxide, it is 0.5% per 1 part by weight. It is preferable that it is 1.5 parts by weight.

Reaction accelerator acts to accelerate the reaction and increase the magnesium content, typical examples of which are amines, 04-0
Examples include 6-diketones and oil-soluble carboxylic acids, but amines are preferred. Examples of amines include ethylenediamine and diaminopropane.

Examples include diaminobutane and triethylenetetramine. However, it is not limited thereto. The amount used is 0 to 1 part by weight of the magnesium oxide used.
．． It is preferably 1 to 1 part by weight.

When the above mixture is heated to 50 to 60°C, carbon dioxide begins to be introduced. The temperature is gradually increased to 100°C. The amount of carbon dioxide introduced is preferably 1 to 3 equivalents per equivalent of magnesium oxide (6). After the introduction of carbon dioxide, the solid precipitate quickly settles when left to cool. This is separated by P by centrifugal filtration or the like. When volatile substances such as hydrocarbon solvents are distilled off from the P liquid, an oil solution of basic magnesium sulfonate is obtained.

Examples 1-4 Petroleum sulfonic acid (molecular weight 500) 50F and mineral oil 3
To the mixture with No. 22, magnesium oxide 352, xylene 174F, hydroxyacetic acid, water, and an amine reaction accelerator were added in the following amounts in order. The reaction mixture was warmed and
Introduction of carbon dioxide was started at 9 o'clock at a temperature of 0 to 60°C. Carbon dioxide was introduced at a rate of 60 l/3 h. During this time, the temperature of the reaction mixture was gradually increased to 90-100.
It was set to ℃. After the introduction was completed, the mixture was allowed to stand and centrifugally filtered. Liquid f was heated to 150° C. under reduced pressure to remove 5 volatile substances. The residual liquid was a basic magnesium sulfonate oil solution, and its properties were as follows.

For comparison, the case where hydroxyacetic acid is not mixed is listed.

As this result shows, mixing hydroxyacetic acid
The filterability is improved, the Mg content of the product is also improved, and a product with a high total base number is obtained.

Example 5 Oil-soluble sodium petroleum sulfonate (average molecular weight 500)
Mineral oil solution with oil content of 60% 821, heavy oil 170 t,
Mg0j2・6H2011, 2f and water 25f, 45
After stirring at ℃ for 3 hours, the aqueous layer was removed. To this were added 35 f1 of magnesium oxide, 10 f1 of hydroxyacetic acid, 312 g of water, and 3.52 g of ethylenediamine. 50% of this mixture
During the temperature raising operation to ~100°C, 60 kg of carbon dioxide were introduced over 3 hours. After that, it was left to cool, left to stand, and centrifugally filtered. r
The liquid was heated to 1501:1 under reduced pressure to drive off volatile oil substances, yielding 295f of residual liquid.

The filterability was good, the Mg content was 6%, and the total base number was 300.

゛ Example 6 Petroleum sulfonic acid (molecular weight 570) 50 r and mineral oil (
9) Magnesium hydroxide 511i in the mixture with 32f? ,
114y of xylene, 10f of didroxyacetic acid, 31g of water
F and 1,3-diaminopropane 4.3 f′(i7
Added sequentially. The reaction mixture was cooled to 50-60°C and the introduction of carbon dioxide was started at a rate of 40,473 hours.
-It is. During this time, the temperature of the mixture was gradually raised to 90-100'C to complete the reaction, allowed to cool and stand, and then centrifugally filtered. The P solution was heated to 150°C under reduced pressure to remove volatile substances, and basic magnesium sulfonate 103r'
fc obtained o Mg content is 5.3%, total base number is 250
Met. Moreover, the filterability was good.

As described above, according to the method of the present invention, the r-permeability is extremely good, and the yield of the basic magnesium sulfonate obtained, its Mg content, and the high total #i & value are easily obtained. The effective Qin Dynasty was obtained.

Patent applicant Kinkai Chemical Co., Ltd. (10)

Claims (1)

[Claims] 1. Passing carbon dioxide through a mixture containing an oil-soluble sulfonic acid or its salt, a stoichiometric excess of magnesium oxide or hydroxide to be reacted with, a hydrocarbon solvent, droxyacetic acid, water, and a reaction promoter. A method for producing basic magnesium sulfonate, characterized by: