JPH0231710B2 - - Google Patents

Description

[Detailed description of the invention]

The invention has a metal ratio of at least 10,
The present invention relates to a method for producing an overbased oil-soluble magnesium salt of sulfonic acid. Overbased oil-soluble magnesium salts of sulfonic acids are used as additives to oil-based compositions such as lubricating oils, greases, fuels, and the like. They can be used as detergents and acid neutralizers, reducing engine wear and corrosion and extending its life. It is difficult to produce highly basic magnesium salts of sulfonic acids in a single step using MgO as the Mg source, and the magnesium salts have a high metal ratio expressed by the amount of magnesium equivalent per equivalent of sulfonic acid of at least 10 to 40. Ta. Previously described processes have resulted in products in which the magnesium is poorly dispersed or unfiltered. (1) A carboxy compound selected from the group consisting of lower carboxylic acids, their anhydrides, substituted lower carboxylic acids, metal salts and esters of lower carboxylic acids, and mixtures thereof, all of which have 1 to 5 carbon atoms. (2) water and optionally (3) an alcohol selected from the group of lower alkanols, lower alkoxyalkanols and mixtures thereof having 1 to 5 carbon atoms. It has been found that overbased magnesium salts of sulfonic acids can be prepared in one step by this method. Such promoter systems provide high quality overbased magnesium sulfonates with very high metal proportions suitable for use in various types of oil-based compositions. Therefore, one object of the invention is to provide at least 10
A method for producing an overbased oil-soluble magnesium salt of a sulfonic acid having a metal ratio of
The object of the present invention is to provide a process in which the product can be prepared in a one-step process in which the reaction mixture is brought into contact with an acid gas. The object of the present invention is to provide a process for producing magnesium sulfonate salts with a very high metal content, in which the overbasing of sulfonic acids is accomplished by using a promoter system in combination with lightweight magnesium oxide. According to the present invention, a method for producing an overbased oil-soluble magnesium salt of a sulfonic acid having a metal ratio of at least 10 comprises: (a) an oil-soluble magnesium salt of a sulfonic acid; (b) a sulfonic acid gas; at least 10 equivalents of light magnesium oxide per equivalent of acid; (c)(1) lower carboxylic acid per equivalent of sulfonic acid;
Essentially oil-insoluble, selected from the group of lower carboxylic acid anhydrides, substituted lower carboxylic acids, metal salts and esters of lower carboxylic acids, all having a total of 2 to 6 carbon atoms, and mixtures thereof. 0.5 to 5 equivalents of carboxyl compound, (2) 2 to 30 equivalents of water per equivalent of sulfonic acid, and (3) lower alcohol per equivalent of sulfonic acid,
an accelerator system consisting of 0 to 35 equivalents of an alcohol selected from the group of lower alkoxyalkanols, all having 1 to 5 carbon atoms, and mixtures thereof; contacting the mixture with a mixture of inert solvents that reduces the viscosity, said contacting being carried out at a temperature from 10° C. to the reflux temperature of said mixture, such that the absorption of acid gas by the reaction mixture is
After reaching the desired level of formation of an overbased oil-soluble magnesium salt of sulfonic acid,
It is characterized by the expulsion of volatile components from the reaction mixture. The acid gas is contacted with the mixture at a temperature between about 10°C (50°C) and the reflux temperature of the mixture. Additional water and/or alcohol can be added continuously or in small portions to the reaction mixture during the period of contacting the mixture with acid gas. The total amount of water used should not exceed 30 equivalents per equivalent of sulfonic acid, and the total amount of alcohol used should not exceed 35 equivalents per equivalent of sulfonic acid. Essentially oil-insoluble carboxyl compounds have the formula
XCOOY [wherein X is -CH ₂ OH, -CH ₂ Cl, -
CH ₂ Br, -CH ₂ COCH ₃ , R or R′NH ₂ , and Y
is H, R or ^Mn , where R is alkyl,
R' represents alkylene, both groups each have from 1 to 4 carbon atoms, the sum of all carbon atoms in R and R' does not exceed 5, and M ⁿ is an alkali metal or alkaline earth metal atom, n
is an integer from 1 to 2]. Preferred oil-insoluble carboxyl compounds of the present invention are acetic acid, propionic acid, butyric acid, glycine, chloroacetic acid, bromobutyric acid, glycolic acid, acetoacetic acid ethyl ester, sodium acetate, calcium acetate,
and magnesium acetate. The compounds can be used separately or in admixture, but the amount of promoter ranges from 0.5 to 5, preferably from 0.7 to 1.3 equivalents per equivalent of oil-soluble sulfonic acid. If more than 5 equivalents of promoter are used, the reaction mixture often becomes very viscous and the product is obtained, but the viscosity of the mixture makes it difficult to isolate the product and during the latter part of the process. It turned out that it was difficult to introduce acid gas into the tank. The initial reaction mixture should have at least a small amount of water per equivalent of sulfonic acid, preferably up to 2 equivalents of water. The mixture is per equivalent of sulfonic acid
Although it is possible to have up to 15 equivalents of water, the preferred range is 2 to 8 equivalents of water in the initial mixture. Although the reaction mechanism is not clear, it is believed that the presence of water in the reaction mixture initiates acid gas absorption by the reaction mixture. However, there is a competitive reaction between the formation of hydroxide of magnesium oxide and water. Therefore, contact of magnesium oxide with water is minimized by adding a small amount of water to the reaction mixture while the gas is in contact with the reaction mixture so that there is water in the system to facilitate absorption of acidic gases. It is preferable to keep it to a minimum. The amount of water used greatly influences the metal ratio value to some extent. The higher the amount of water used, the higher the metal ratio. However,
If the amount of water is high, there will be a resulting cloudiness in the product. On the other hand, lack of water increases the viscosity of the reaction mixture and lowers the metal proportion. The total amount of water added to the mixture during the entire reaction time should not exceed 30 equivalents per equivalent of oil-soluble sulfonic acid. The optimal amount of water used is the amount of magnesium oxide used,
Depends on the desired metal ratio. This is because the higher the amount of water, the higher the metal ratio product can be obtained. It depends on the intended use of the product, but if it is used for something like bunker fuel oil, there is no problem even if the product is cloudy. However, extremely clear products are desired for lubricating oils. The alcohols used in this method include lower aliphatic alkanols, alkoxyalkanols, and mixtures thereof. However, the number of carbon atoms must not exceed 5. Examples of alcohols are methanol, ethanol, isopropanol, n-propanol, butanol and pentanol. The preferred alcohol is methanol. This is because it is cheap and easy to remove from the reaction mixture. Examples of alkoxyalkanols include:
There are methoxyethanol and ethoxyethanol. The presence of alcohol in the initial mixture is not required to initiate the absorption of acid gas into the reaction mixture. However, it is believed that the main function of the alcohol is to increase the stability of the colloidal dispersion of the magnesium salt in the oil. For this reason, the initial reaction mixture may contain no alcohol at all or only a small amount. Then, while in contact with the acid gas, add the remaining amount of alcohol, alone or together with water. It was found that when the amount of alcohol added exceeds 35 equivalents per equivalent of sulfonic acid, the metal ratio becomes low. The preferred amount used is between 4 and 20 equivalents per equivalent of sulfonic acid. The sulfonic acid used in the method of the present invention is widely known as an oil-soluble sulfonic acid, and can be derived from natural petroleum fractions, or can be a sulfonated compound prepared by various synthetic methods.
Typical oil-soluble sulfonic acids are alkanesulfonic acids, aromatic sulfonic acids, alkaryl sulfonic acids,
Aralkylsulfonic acids, petroleum sulfonic acids, such as mahogany sulfonic acid, petroleum sulfonic acids, paraffin wax sulfonic acids, petroleum naphthenesulfonic acids, polyalkylated sulfonic acids, and sulfonic acids obtained by treatment of petroleum fractions with fuming sulfuric acid. It is. It goes without saying that mixtures of these sulfonic acids can be used for the production of basified magnesium sulfate. The process of the invention can be operated with low concentrations of sulfonate. In this case, it becomes possible to use an oil-based raw material composition containing only a small amount of magnesium sulfonate, such as 10% by weight, without further concentrating the oil-based raw material. As is well known, a variety of acidic gases can be used to basify the magnesium sulfonate. Preferred acidic gases include carbon dioxide gas, sulfur dioxide gas, nitrogen dioxide,
It is hydrogen sulfide. The gases are bubbled into the reaction mixture and mixed, so that the selected gases first come into contact with the components of the mixed reaction mixture. In a preferred embodiment, the contact temperature between the reaction mixture and the gas is between 10°C (50〓) and 95°C (200〓), preferably 48°C.
It can vary from ℃ to 77℃ (120 to 170〓). The magnesium oxide used in a preferred embodiment of this method is in light or active form. Here, "light" refers to something that can be obtained in a very bulky form, whereas something that can be obtained in a dense form is called "heavy" (“Merck
10th edition, p. 5507). These magnesium oxides are commercially available under the following trademarks.
"MAGNESITE" (Martin Murrieta Chemicals; Hunt Barry, Maryland),
"MICHIGAN No.3", "MICHIGAN No.15",
"MICHIGAN No.340" (Michigan Chemical
Corp; Illinois, Chicago), “DOW L-2”,
"DOW C-1" (Dow, Chemicals; Michigan,
Midland), “ELASTOMAG 170”,
"ELASTOMAG 20" (Morton, Chemicals;
(Chicago, Illinois), “MGLITE Y” (Wuitatker, Clark, &Daniels; South Plainfield, New York), “LYCAL
93/711'', ``LYCAL 96/575'' (Pigment, Chemicals; Toronto, Canada), and ``MAGOX PREMIUM'' (Basics, Chemicals; Cleveland, Ohio). The amount of magnesium oxide used depends on the desired proportion of metal in the final product. The metal ratio is the ratio of equivalents of magnesium in the overbased compound to one equivalent of sulfonic acid in the overbased compound. Therefore, to obtain a metal ratio of, for example, 30, at least 30 equivalents of magnesium oxide must be used for each equivalent of sulfonic acid in the initial reaction mixture. If this invention is carried out under unfavorable conditions due to inefficiency, an overbased magnesium sulfonate salt structure can be obtained by using an excess of magnesium oxide than determined by the metal ratio. It goes without saying that sufficient supplementation of magnesium should be ensured. Several types of volatile and non-volatile diluents can be used in this method. Non-volatile diluents are usually mineral or synthetic lubricating oils, e.g.
A lubricating oil with a viscosity of 100SUS or higher. Inert volatile diluent preferably from 65°C
It is a hydrocarbon with a boiling point in the range of 149°C. They can be aliphatic, aromatic solvents or mixtures of both types. For example, naphtha is a particularly useful diluent. Other types of suitable diluents include Stoddard solvents, cycloaliphatic and aromatic hydrocarbons and corresponding halogenated hydrocarbons, such as chlorobenzene and the conventional solvents commonly used in overbasing processes such as those in this invention. It is an organic diluent. The amount of diluent used is sufficient to reduce the viscosity of the reaction mixture early in the reaction to promote mixing of the reaction mixture and to facilitate contact of the mixture with acid gas. The length of time that the reaction mixture is in contact with the acid gas depends on the desired amount of magnesium in the overbased magnesium sulfonate. Contact of the gas with the mixture continues until no more gas is absorbed. The lack of absorption indicates that substantially all of the magnesium oxide initially introduced into the system has reacted to overbased magnesium sulfonate. In order to determine when gas absorption has ended, the flow rate of the acidic gas introduced is compared with the flow rate of the exhaust gas. Absorption is substantially complete when the exhaust gas flow rate is approximately the same as the inlet gas flow rate. It will be appreciated that according to the present invention, impurities and other changes in the chosen petroleum feedstock and magnesium oxide may result in products with slightly different metal proportions than those achieved in the following example. become. Accordingly, the following examples are merely illustrative of the invention, and the scope of the invention is not thereby limited. Product 1: Put 310 gm of solvent-refined lubricating oil with a viscosity of 330 SUS at about 38°C into the reactor of 1, equipped with a stirrer, dropping funnel, thermometer, condenser, and water bottle, and stir vigorously for half an hour. 25% by weight of sulfuric acid
103gm was added to make oil-soluble magnesium sulfonate. The temperature was maintained at 32-44°C. The mixture was stirred for a further 10 minutes and then cooled with 25 gm of water.
310 gm of VM ₊ P naphtha was added and the mixture was left in the dropping funnel for 3 hours. 80gm of acid was separated and removed. The organic naphtha layer was washed with 120 gm of water and the yellowish lower aqueous layer was separated and discarded. 100gm water, 10gm methanol and 8gm in the upper sulfonic acid/naphtha layer
of magnesium oxide was added. The mixture was stirred and left at 60°C while the sulfonic acid was neutralized. The separated lower aqueous layer was discarded, and the solvent and water were removed from the naphtha layer to obtain a 30% by weight oil solution of magnesium sulfonate. Example 1 85 gm of product 1 magnesium sulfonate and 25 gm of lubricating oil of 100 SUS viscosity at 38° C. in a 1000 ml flask equipped with stirrer, thermometer, condenser, dropping funnel and perforated cylindrical dispersion tube. naphtha
Add 140gm and 30gm of magnesium oxide (MAGNESITE No.569). The mixture was heated to about 54° C. and 6 gm of magnesium acetate was added. Heating was continued at about 55° C. and a mixture of water/methanol, 20 gm/16 gm each, was added dropwise through a separatory funnel over 66 minutes. Carbonation was initiated by introducing carbon dioxide into the reaction mixture at a rate of 75 ml/min and continued for 3 hours. The carbonated product was filtered using diatomaceous earth filter aid. Then add water, methanol and naphtha to approx.
It was removed by heating to 205°C. A clear product with a magnesium content of 9.2% was thus obtained. This corresponds to a metal ratio of 27.0. Example 2 The following reactants were mixed in a 1000 ml flask equipped with a mechanical stirrer, thermometer, condenser, and perforated tubular dispersion tube. 137 g naphtha (BP 115-144°C) 8 gm methanol 4 gm water 32 gm lubricating oil 100 gm magnesium sulfonate solution (consisting of 45% magnesium sulfonate, 42% lubricating oil, 13% naphtha. Used to make magnesium sulfonate Sulfonic acid is a linear alkylbenzene sulfonic acid with a molecular weight of approximately 500 obtained from continental oil.) 30gm Magnesium Oxide (MAGNESITE No.
569; manufactured by Martin Murrieta) and hydroacetic acid
5.25 g of this mixture was heated to near reflux temperature (approximately 66° C.) and added into the mixture through the dispersion tube at a flow rate of 100 ml/min while stirring. Carbonation lasted for 2 1/2 hours, with an additional 8 g of water and 8 g of methanol added 40 minutes after the start of carbonation, and an additional 4 g of water and 8 g of methanol added 80 minutes after the start of carbonation. Ta. The carbonated product was filtered with diatomaceous earth filter aid. The volatile components of the solvent, water, methanol, and naphtha were removed by heating to about 205°C. _CO2 gas was introduced into the heated mixture to completely remove the solvent. The final product thus obtained was a clear oil-soluble solution containing 9.4% by weight of magnesium.
Magnesium sulfonate is 26.5% by weight, approximately
It had a viscosity of 525 SUS at 99°C, and the metal ratio of the product was 14.8. Example 3 This example illustrates temperature effects during carbonation. Example 2 The same procedure was followed, but the temperature of the mixture was maintained at 32-44°C. The final product is a clear oil-soluble solution containing 6.9% magnesium by weight;
It contained 26.9% by weight of magnesium sulfonate. The metal ratio was 10.7. Examples 4-7 The results of a series of experiments are shown in the table below, which describes the relationship between the amount of methanol and water used during the carbonation process and the metal ratio. Example 2 Addition of water/methanol at 0, 40 and 80 minutes during carbonation
I went in the same way. Examples 8-11 Table 2 summarizes the results of a series of experiments illustrating the addition of water/methanol at various time intervals. Examples 12-23 The results of this series of experiments illustrate the relationship between product quality and catalyst usage. The results of these experiments are shown in Table 3. The method for each experiment was the same as in Example 2. Examples 24-29 Table 4 shows the results of a series of experiments illustrating the use of different catalysts. The treatment conditions in each experiment were the same as in Example 2, except that equivalent moles of the various catalysts listed in the table were used. Examples 30-33 These examples demonstrate how sulfonic acids affect product quality when using this method to produce lubricating oils containing magnesium. The results of this experiment are summarized in Table 5. The process of each experiment was similar to that used in Experiment 2. Examples 34-46 The results of these experiments are summarized in Table 6 and illustrate the effect on products obtained using various commercially available magnesium oxides. The experimental process was the same as in Example 2. Examples 47-49 These experiments illustrate the use of various lower alcohols in the manner described in Example 2.
The experimental results are summarized in Table 7. These experimental results demonstrate that good quality basicized magnesium salts of sulfonic acids can be produced and used in lubricating oils, greases, and other oil-based products, such as fuel oil, barker oil, etc., with metals ranging from 5 to 40. It can be seen that it can be used as a ratio additive. This product is permanently soluble in organic environments and can therefore be used as an additive in the lubricant and fuel sector. Although various preferred embodiments of the present invention have been described in detail above, it goes without saying that various modifications may be made without departing from the spirit of the invention or the scope of the claims.

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[Table] Difluormate

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[Table] Liquid products

Claims (1)

[Claims] 1. A method for producing an overbased oil-soluble magnesium salt of a sulfonic acid having a metal ratio of at least 10, comprising: (a) an oil-soluble magnesium salt of a sulfonic acid; at least 10 equivalents of light magnesium oxide per equivalent of sulfonic acid; (c)(1) lower carboxylic acid per equivalent of sulfonic acid;
Essentially oil-insoluble, selected from the group of lower carboxylic acid anhydrides, substituted lower carboxylic acids, metal salts and esters of lower carboxylic acids, all having a total of 2 to 6 carbon atoms, and mixtures thereof. 0.5 to 5 equivalents of carboxyl compound, (2) 2 to 30 equivalents of water per equivalent of sulfonic acid, and (3) lower alcohol per equivalent of sulfonic acid,
an accelerator system consisting of 0 to 35 equivalents of an alcohol selected from the group of lower alkoxyalkanols, all having 1 to 5 carbon atoms, and mixtures thereof; contacting the mixture with a mixture of inert solvents that reduces the viscosity, said contacting being carried out at a temperature from 10° C. to the reflux temperature of said mixture, such that the absorption of acid gas by the reaction mixture is
After reaching the desired level of formation of an overbased oil-soluble magnesium salt of sulfonic acid,
A process for producing an overbased oil-soluble magnesium salt of a sulfonic acid, characterized in that volatile components are expelled from the reaction mixture. 2. Use of 10 to 40 equivalents of lightweight magnesium oxide per equivalent of sulfonic acid to produce an overbased oil-soluble magnesium salt of sulfonic acid with a metal ratio of 10 to 40. Method described. 3. Use of 20 to 40 equivalents of lightweight magnesium oxide per equivalent of sulfonic acid to produce an overbased oil-soluble magnesium salt of sulfonic acid with a metal ratio of 20 to 40. Method described. 4. The method according to any one of claims 1 to 3, wherein 0.7 to 1.3 equivalents of the carboxyl compound are used. 5. 2.5 to 28 equivalents of additional water are added to the mixture during the time that the acidic gas is in contact with the mixture, and the total amount of water in the mixture is up to 30 equivalents, according to claim 1 or 2. the method of. 6. A sufficient amount of the selected alcohol is present in the mixture to initiate absorption of carbon dioxide, and during the time that the acidic gas is in contact with the mixture, 2 to 28
Any one of claims 1 to 3, wherein an equivalent of additional water and an amount of the selected alcohol are added up to 35 equivalents, the total amount of alcohol in the mixture being up to 35 equivalents. Method described. 7. The method according to claim 5, wherein the acidic gas is carbon dioxide. 8. The method of claim 5, wherein the amount of water present in the mixture before contacting the mixture with the acid gas is from 2 to 15 equivalents. 9. The method of claim 5, wherein the amount of water present in the mixture before contacting the mixture with the acid gas is from 2 to 8 equivalents. 10. The method according to claim 6, wherein the total amount of alcohol used is 4 to 20 equivalents. 11 Alcohol is methanol, ethanol,
4. The method according to any one of claims 1 to 3, wherein the alcohol is selected from the group consisting of isopropanol, n-propanol, butanol, pentanol, methoxyethanol and ethoxyethanol. 12 The carboxyl compound has the formula: XCOOY [wherein X is _-CH2OH , _-CH2Cl , _-CH2Br , -
CH ₂ COCH ₃ , R or R′NH ₂ and Y is H, R
or M ⁿ , where R is alkyl and R' is alkylene, and both groups each have 1 to
4 carbon atoms, the sum of all carbon atoms in R and R′ does not exceed 5, M ⁿ is an alkali metal or alkaline earth metal atom, and n is an integer from 1 to 2. ] Claim 1 indicated by
The method described in any one of paragraphs to paragraphs 3 to 3. 13 The carboxyl compound is acetic acid, propionic acid, butyric acid, glycine, chloroacetic acid, bromoacetic acid,
13. The method of claim 12, wherein the compound is selected from the group consisting of glycolic acid, ethyl acetoacetate, sodium acetate, calcium acetate, magnesium acetate, and mixtures thereof. 14. The method according to claim 13, wherein the carboxyl compound is acetic acid, magnesium acetate, or glycine. 15. The method according to claim 11, wherein the alcohol is methanol. 16 To prepare overbased oil-soluble magnesium salts of sulfonic acids with metal ratios of 10 to 40, sulfonic acids are mixed with 0.5 to 5 equivalents of carboxyl compound per equivalent of sulfonic acid and water per equivalent of sulfonic acid. 2 to 8 equivalents of light magnesium oxide per equivalent of sulfonic acid in the presence of an accelerator system consisting of up to 8 equivalents of alcohol per equivalent of sulfonic acid.
additional water and alcohol are added to the reaction mixture at intervals of time while the acidic gas is in contact with the mixture, such that the total amount of water in the mixture is less than 30 equivalents; The total amount of alcohol is less than 35 equivalents, and after absorption of acid gas by the reaction mixture, the overbased oil-soluble of the sulfonic acid has a metal ratio of 10 to 40 of the number of equivalents of magnesium to the number of equivalents of the sulfonic acid. 2. The method of claim 1, wherein volatile components are driven from the reaction mixture at the desired level to produce magnesium salts. 17. The method of claim 16, wherein the acid gas is contacted with the mixture at a temperature of 48 to 95°C. 18. The method according to claim 16, wherein 0.7 to 1.3 equivalents of the carboxyl compound are used. 19 Carboxyl compound selected from the group consisting of acetic acid, propionic acid, butyric acid, glycine, chloroacetic acid, bromoacetic acid, glycolic acid, ethyl acetoacetate, sodium acetate, calcium acetate, magnesium acetate, and mixtures thereof 0.7 to 1.3
17. A method according to claim 16, in which equivalent amounts are used. 20. The method according to claim 16, wherein the carboxyl compound is acetic acid or glycine. 21. The method according to claim 16, wherein the reaction accelerator is acetic acid. 22. The method of claim 16, wherein additional water and alcohol are added in portions or periodically to the reaction mixture during the time that carbon dioxide as acid gas is in contact with the mixture. 23. The method of claim 16, wherein carbon dioxide as an acidic gas is contacted with the mixture until absorption of carbon dioxide by the mixture is substantially complete.