DE2233539A1 - PROCESS FOR PRODUCING A STABLE DISPERSION OF AN INORGANIC METAL COMPOUND - Google Patents

Description

Process for the preparation of a stable dispersion of a inorganic metal compound

The invention relates to a method for producing a stable dispersion of an inorganic metal compound in a metal-free, oil-soluble, ash-free dispersant compound, which contains acylated nitrogen. In particular, it relates to ashless detergent-dispersant additives for Lubricating oils and a process for the production of highly basic (overba.sed) dispersions in which the dispersant is a

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metal-free, acylated nitrogen-containing compound.

Highly basic dispersions have already been proposed which can be used as additives for detergent-type lubricating oils for dispersing harmful insoluble particles formed during the combustion of the fuel and the oxidation of the oil and to neutralize harmful acidic combustion product en and acidic varnish precursors can be used. The last-mentioned effect is based on the high reserve basicity, which is a characteristic of the highly basic dispersions used as additives.

Various types of highly basic dispersions have already been proposed for the use mentioned as a lubricating oil additive been. Such additives include, for example, highly basic soaps, alkylphenates, alkylphenol sulfides and metal salts of organic sulfonic acids. The organic sulfone

the

Acid dispersions can be made highly basic in a wide variety of ways, but the general procedure is to suspend fine particles of a metallic neutralizing agent, such as a metal oxide, metal hydroxide or metal carbonate, therein. In this process, a dispersion is obtained which contains an excess amount of metal theoretically required to replace the acidic hydrogen of the acid used as the starting material and which acts as a dispersant after neutralization. Highly basic sulfonate dispersions are used to a large extent in lubricating oils because of their high temperature performance. However, their dispersing capacity at lower temperatures is not optimal for many uses as a lubricating oil additive and therefore other additives have often been used in conjunction with the sulfonate additives in order to improve the lubricating oils.

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to give excellent dispersing power at low temperatures. One of the most useful representatives of this type recently proposed are nitrogen-containing derivatives of alkenyl succinic acids and succinic anhydrides. These so-called ashless dispersants complement the highly basic sulfonates and are advantageously characterized by that they form little or no ash on oxidation or combustion of the oils in which they are contained.

In various recently published patents it has already been proposed to make the nitrogen-containing succinic acid derivatives highly basic for the production of valuable ones Lubricating oil additive preparations that have a reserve basicity independent of the other additives, for example the sulfonates exhibit. For many purposes it is thus possible omitting the highly basic sulfonates without sacrificing sufficient performance at high temperature is, and this has the advantage that the ash content of the finished Lube mixture and the sticky engine debris used for Lubricating oils containing highly basic sulfonate additives are characteristic. In U.S. Patent 3,451,931 proposed to make high molecular weight succinic acid derivatives of the type described highly basic by making a basic Metal compound suspended in the derivative and the suspension with an acidic gas, such as. Carbon dioxide, treated. This creates a colloidal dispersion of the metal salt with a high basicity and good dispersibility. According to the US patent 3 306 908 a metal complex is produced by reacting certain specific salts of metals with the Atomic numbers from 24 to 30 with the nitrogen-containing succinic acid derivative. Although the value of the metal complex so formed is explained as a lubricating oil additive - contains this patent specification

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no information is given about its ability to make basic, but it is pointed out that the metal in the complex is not is in free form so that it could easily perform an acid neutralization function, by pointing out that the chemical bond between the metal and the nitrogen-containing succinic acid derivative is a permanent bond.

A slightly different product that is not concerned with making a nitrogen-containing succinic acid derivative highly basic, the but still a highly basic lubricating oil additive derived from succinic acid is disclosed in U.S. Patent 3,567,637. In this case, the additive is made by neutralizing a long-chain alkenyl substituted succinic anhydride or a succinic acid with a basic inorganic alkaline earth compound in the presence of a lower alkanol. This leads to the neutralization of the acid or the anhydride and a simultaneous incorporation a stoichiometric excess of alkaline earth metal compound in the dispersion obtained. Be through the dispersion then sufficient amounts of gaseous carbon dioxide are passed to remove the excess basic alkaline earth metal compound to convert to a carbonate. Ammonia is used as a catalyst.

The aim of the invention is now to provide a method for producing a indicate highly basic ashless dispersant additive preparation that is suitable for incorporation into lubricating oils, to give them reserve basicity and high dispersibility. The aim of the invention is in particular to provide a method with the help of which it is possible to develop a nitrogen in a simple, economical and effective manner.

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- To make Sc containing derivative of succinic acid or succinic anhydride with a molecular weight highly basic.

Further features, details and advantages of the invention emerge from the following description of preferred embodiments.

The present invention relates generally to an improved process for the preparation of highly basic nitrogen containing Carboxylic acid and carboxylic acid anhydride derivatives, which are very suitable as ashless dispersants and lubricating oils, to which they are added give a reserve base. According to this method, it is advantageously possible to obtain a large amount of very fine particles of basic alkaline earth metal compounds to be dispersed or peptized evenly in the additional preparation. This means that the Making the nitrogen-containing carboxylic acid derivatives highly basic of the type described as a result of the requirement for a maximum Solubilization of the basic in the form of oxides or hydroxides in the nitrogen-containing derivative Metal connections occurring difficulties avoided.

According to the invention, a highly basic (overbased) dispersion, which is suitable as a lubricating oil additive, prepared by adding an acylated nitrogen atom to a solution metal-free, oil-soluble, neutral or basic dispersant in an alcohol or an alcohol / aromatic mixture adding a metal alkylate carbonate complex. The dispersant is preferably an amide Imide or an ester resulting from the reaction of an alkenyl carboxylic acid or a high molecular weight acid anhydride with a nitrogen-containing organic compound

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with at least one amino or hydroxy group. Simultaneously or after the addition of the alkylate carbonate complex the complex hydrolyzes to form a dispersion of fine particles of the metal carbonate. The solvents are then stripped from the dispersion to form a light, clear composition with a base number of about 50 up to about 250, which is suitable as an ash-free detergent-dispersant additive to lubricating oils.

The invention is based on a method of the type mentioned and is characterized in that one

a mixture which (a) from about 10 to about 60% by weight of a non-volatile, soluble carrier material having a boiling point above about 150 ° C and (b) about 90 to about 40 weight percent of one metal-free, acylated, nitrogen-containing ash-free, oil-soluble dispersant compound with an organic Solvent from the group of monohydroxy alcohols with 1 to 4 carbon atoms and the mixtures of such alcohols with monocyclic aromatic hydrocarbons in which the alcohol / aromatic mixture at least 25 wt .-% of one or contains a plurality of the alcohols in a weight ratio of the organic solvent to the mixture of the oil-soluble Mixes carrier material and the dispersant compound of at least 1.25: 1,

the mixture of the organic solvent, the non-volatile The carrier material and the dispersant compound are heated to a temperature of about 25 to about 100 C,

to the heated mixture of the solvent, the oil-soluble carrier material and the dispersant compound about 5 to about 35% by weight of a metal alkylate carbonate complex with calcium,

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Magnesium or barium is added as a metal component while the temperature of the mixture is between about 25 and about 100 ° C holds, wherein the addition of the complex in the presence of such an amount of water in the mixture of the solvent, the oil-soluble carrier and the dispersant, which are used to hydrolyze the metal alkoxide carbonate complex stoichiometrically 'required amount and about 0.5 to about 6.0 wt .-%, based on the total weight of the mixture inclusive of the water and the complex, matter, and

from the reaction mixture to which the complex has been added, at least all ι
Materials removed.

is, at least all volatile below about 125 G boiling

The method according to the invention is generally carried out in such a way that first a solution of an oil-soluble, acylated nitrogen-containing dispersant in a monohydroxy alcohol with 1 to 4 carbon atoms or in a solvent that one or more such alcohols and one aromatic monocyclic hydrocarbon such as benzene, toluene or xylene. Preferred dispersants are Amides, imides or esters are used, which are obtained by reacting an alkenyl carboxylic acid or an anhydride with a high molecular weight with a nitrogen-containing organic compound having at least one amino or hydroxy group. Succinic anhydride is preferably used as one of the reactants with a high molecular weight is used.

The dispersant solution is, to a temperature of about 25 to about 100 ° C and heated with an oil-soluble metal alkoxide carbonate complex and water in a stoichiometric excess with respect to the stoichiometric excess required to hydrolyze the complex

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mixed amount. As the metal in the metal alkylate carbonate complex Magnesium, calcium or barium are used. After hydrolyzing the complex using the water present the mixture is heated to remove the volatile solvents. An important aspect of the present invention is the identification of the solvent system in which the dispersant is used can be solved at the beginning and which has proven to be critical for the implementation of the invention. The usage a monohydroxy alcohol having 1 to 4 carbon atoms or such an alcohol together with a monocyclic aromatic hydrocarbon appears to be essential for the Manufacture of a suitable highly basic product. A solvent is preferably used which contains equal parts by weight of alcohol and aromatics.

As already indicated, there is the initial stage of the invention Method in that one contains a solution of certain oil-soluble, metal-free, an acylated nitrogen atom Compounds in an alcohol or in a mixture of an alcohol and a monocyclic aromatic hydrocarbon manufactures. Particularly suitable compounds are the esters, amides, and imides derived from high molecular weight carboxylic acids are derived. The derivative functions in the highly basic additional preparation obtained in the process as a dispersant / detergent and is characterized by the fact that it is a neutral or weakly basic oil-soluble material represents with a relatively high molecular weight. The production of these materials is known per se and in the U.S. Patents 3,451,931, 3,338,831, 3,376,864 and 3,172. In the method according to the invention as Starting material used, nitrogen-containing dispersing agent

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agent is preferably derived from the reaction of an alkenylsuccinic acid or a succinic anhydride with a nitrogen-containing organic compound having at least one amino or hydroxy group, including compounds such as alkylene polyamines and hydroxyalkylamines. The alkenyl succinic anhydrides can be easily prepared by thermal condensation of maleic anhydride with a branched polyalkene such as polybutene. A polymer with a relatively high molecular weight, which is an alkenyl succinic anhydride, is obtained by thermal condensation. In general, this polymer has a molecular weight of about 600 to about 4000. The succinic anhydride produced in this way is then reacted with an organic compound containing nitrogen, preferably a polyamine, such as diethylenetriamine or tetraethylene pentamine. The dispersants obtained in the reactions described can be amides, imides or esters with a molecular weight of about 4,000 to about 10,000. Often times the dispersant will contain a mixture of imides, amides and esters formed by the reaction of succinic acid or succinic anhydride with the nitrogen-containing organic compound, and in a given dispersant composition the amide or the imide may predominate. It should be noted in this context that the Dispergiermittelausgangsmaterialien are preferred as in the inventive process used _# nitrogen-containing derivatives of alkenyl succinic acids and succinic anhydrides also known as the process for their preparation. A number of these materials are commercially available.

An essential aspect of the present invention is that for

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- ίο -

Dilute the nitrogen-containing, high molecular weight, ashless Dispersants of the invention. Solvent system used at the beginning of the process of the invention. The in Commercially available or freshly made dispersants are almost always used in an oil-soluble, non-volatile (above 150 C boiling) carrier material, which is a naphthene or paraffin oil, such as pale oil can. The amount of carrier material is usually from about 10 to about 40 percent by weight. If desired, the amount of non-volatile carrier material increased to about 60 wt .-% will. It has been found that it is critical for the successful implementation of the method according to the invention that the solution of the dispersant in the non-volatile carrier material in a mixture with a monohydroxy alcohol with 1 to carbon atoms or with a mixture of such alcohols a monocyclic aromatic hydrocarbon is used. The mechanism responsible for ensuring that the Use of the alcohol or an alcohol / aromatic solvent is critical, is not yet known exactly. However, it is believed that this type of solvent has the effect that Hydrolysis of the metal alkoxide carbonate complex will effectively proceed to leave and in the hydrolysis very small, uniformly dispersed particles in the dispersant material to form the highly basic metal compound.

Examples of alcohols that can be used are methanol, Ethanol, isopropanol, n-propanol, isobutanol, n-butanol and certain monoethers of ethylene glycol including the monoethyl ether of ethylene glycol sold under the trade name Cellosolve, and monomethyl ether from Ethylene glycol, sold under the trade name Methylcellosolve

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is available. Examples of suitable raonocyclic aromatic Hydrocarbons are benzene, xylene and toluene.

I) the amount of solvent used will of course vary depending on the alcohol used as the solvent or the mixture of the alcohol with an aromatic hydrocarbon and depending on the particular dispersant used. In general, however, a weight ratio of about 1.25 applies: 1 to about 2.5: 1 of solvent to dispersant 'non-volatile carrier starting material as both a minimum and a minimum as the preferred amount of solvent. Of course, larger amounts of solvent can also be used, but this is beneficial no additional benefit. An example of a preferred solvent / dispersant system is a pale oil solution of an alkenyl succinimide with a molecular weight of about 5000 to about 9000 and one of equal parts by weight a solvent consisting of a monohydroxy alcohol having 1 to 4 carbon atoms and benzene. The weight ratio of Dispersant to oil feed to alcohol and benzene in this preferred system is about 1: 1: 1.

For making the dispersant highly basic by suspending small particles of the basic metal compounds therein becomes a certain amount of an oil-soluble metal alkylate carbonate complex introduced into the dispersant solution and hydrolyzed in situ to make the complex highly basic To transfer metal compounds. This method for making high-base (overbasing) has compared to the previous Making such nitrogen-containing succinic acid derivatives highly basic has the advantage of doing so a greater total amount of highly basicizing metal lighter

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can be suspended in the dispersant. Although the general mechanism involved and the ones to be expected Advantages of using oil-soluble complexes of the type described for making lubricating oil additives highly basic had already been recognized, this finding related to the application of this process for rendering oil soluble ones highly basic Sulphonate-type additives. Applying this procedure for making ash-free dispersants highly basic of the acylated nitrogen containing type has not been known heretofore. It was found that this general Method for making highly basic, as was previously the case for making highly basic of high temperature sulfonic acid dispersants has been applied, must be changed in an unexpected manner so that thereafter the described nitrogen-containing succinic acid derivatives can be made highly basic.

As already indicated, those are placed on the solvent system Unexpected requirements and paraffin solvents, such as hexane or heptane, used to make sulfonic acid dispersants highly basic are suitable do not work effectively in the method of the invention. About that in addition, the amount of water used to effectively achieve hydrolysis of the metal alkoxide carbonate complex is generally lower than that used to make highly basic of sulfonates is used. This is explained in more detail below explained.

In the case of the metal alkylate carbonate complexes used according to the invention they are of the type described in U.S. Patents 3,150,088 and 3,150,089. These metal alkoxide carbonate complexes have the general formula:

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Il

₉₉ 5 ^ 0-C-OCH ₉ CH ₉ OR)

in which M is a divalent metal ion from the group consisting of calcium, magnesium and barium and R is an alkyl group with 1 to 6 Carbon atoms or an organic radical of the formula:

HH

-CCOR ¹

II: ...
HH

in which R ^{1 is} an alkyl group having 1 to 4 carbon atoms and χ is a number from 0.5 to 1.5, preferably from 0.75 to 1.0 ». The process for preparing these complexes is described in more detail in the patents mentioned.

The water used to hydrolyze the complex dissolved in the dispersant can be added to the dispersant or better added simultaneously with the complex. The water added to the dispersant solution must be in one stoichiometric excess compared to the theoretical for Hydrolyze all of the added metal alkylate carbonate complex required quantity. This prevents and supports the formation of undispersed solids the recovery of organic volatiles that remain in the mixture after bashing. The total amount of water actually used varies to some extent depending on the Metallalkylatcar- used in each case for making highly basic. bonat complex. In the case of a calcium-containing complex, about 1.5 to about 4 moles, preferably 1.6 to 2.4 moles Water used per mole of the complex. Magnesium contains

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From about 2 to about 4, preferably from 3 to 3.5 moles of water per mole of complex are used tend complexes. In case of Barium complexes are preferably used from about 2 to about 4 moles of water per mole of complex added. As already stated, it is preferred to add the water to the dispersant / alcohol solution simultaneously with the addition of the complex admit. It is also useful to use the water in the form of an azeotrope of water with a monoether alcohol Add 3 or 4 carbon atoms such as Cellosolve or Methylcello solve.

The amounts of metal alkylate carbonate complex and oil-soluble dispersant used in the highly basicization process and non-volatile carrier material will vary according to the amount of that desired in the final composition Dispersant (hereinafter referred to as "percentage activity") and depending on the degree of reserve basicity desired or the basification that is sought. This latter property is defined by the base number the final composition as determined by acetic acid titration. In general, oil-soluble, metal-free, nitrogen-containing Materials which the present invention used Represent dispersants, are not made as highly basic as oil-soluble sulfonate dispersions and from this The basis for a given weight (% activity) of the dispersant is only about half as much metal alkylate carbonate complex used to achieve maximum overbasing as in the use to achieve a maximally basifying an equivalent amount of high temperature oil soluble sulfonic acid dispersants. To the method according to the invention, preparations with bases can

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2233533

- 15 numbers of up to about 250 can be produced.

To further explain the process according to the invention, the following are the amounts of different amounts in the course of the process materials introduced into the reaction mixture within the appropriate (general) and preferred ranges given in% by weight:.

general (suitably preferred) area area

4-35 6-20 5-40 10-30 5-35 10-20 0.5-6.0 0.9-3.5 35 - 85 45-70

Dispersant Non-Volatile Carrier ⁺

Metal alkylate carbonate complex

water

Volatile solvent

⁺ This also includes a non-volatile oil present in the dispersant produced or available on the market

this comprises the initial dispersant solution of an alcohol or an alcohol and an aromatic hydrocarbon, as described above, and a process solvent with a boiling point below 175 C, d, according to the method is added.

with a boiling point below 175 C, which during the

After the solution of the dispersant in alcohol or in an alcohol / benzene mixture and water or an additional inert, non-volatile carrier material that is in at this stage is to be incorporated, the solution is stirred to a temperature of about 25 heated to about 100 C. The solution is preferably maintained at a temperature of from about 30 to about 65.degree. While . "

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the dispersant solution has the temperature described, the metal alkoxide carbonate complex slowly becomes the solution admitted. If all of the required water has not been previously added to the solution, it will be at the same time added to the addition of the complex, and this simultaneous addition is preferred. As indicated above, it is also useful that the added water is in the form of a water / monoether alcohol azeotrope is present. After the addition of the metal alkylate carbonate complex (which is preferably in the form an alcoholic solution of the complex ■ is added) the dispersant solution in the manner described are the volatile solvents, including alcohol or the alcohol / benzene solvent for the dispersant, the alcohol formed on hydrolysis of the complex and Water, removed from the reaction mixture. Although in some cases the solvent removal is practically complete Distillation can take place, it is preferred to pass an inert gas through the reaction mixture in order to remove the to ease the last portions of the solvent ^ and in the The gas used for this purpose is preferably carbon dioxide or a mixture of carbon dioxide and nitrogen. In general, to remove the solvent, the reaction mixture is heated to temperatures up to about 125 to 190 ° C and then stripped at this temperature by CO. The distillation is preferably careful carried out to the formation of a gel or the development to prevent a haze (cloudiness) within the reaction mixture ^ and, if desired, to remove the contents of the To keep reaction mixture fluid, use small amounts of light hydrocarbon process solvents that are below boiling about 175 C and preferably below about 150 C, against

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Added at the end of the distillation. Suitable process solvents are e.g. petroleum naphtha, hexane, »heptane, octane, Benzene, toluene and xylene. Hexane is particularly "well suited."

The amounts of oil-soluble, nitrogen-containing, metal-free dispersant, non-volatile carrier oil, and basic Alkaline earth metal compounds in the end product preparations are in the table below in parts by weight specified: ·

General area Dispersants "15 - 70 Λ. More preferred
area Non-volatile carrier 5 - 80 25-50 Basic metal compound
(as metal) 5 - 25th 35-65 8-15

The highly basic preparations produced by the process according to the invention are stable dispersions which are liquid, relatively clear and bright in transmitted light. The dispersions can be added to engine lubricating oils to effectively disperse the solid particulate products of fuel combustion and engine oil degradation and to neutralize the acidic products formed during engine operation.

The following examples are intended to explain the invention in more detail without, however, restricting it thereto.

example 1

A commercially available preparation or composition contains a succinimide of the general formula

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NR ¹
C.

in which R is an alkenyl radical and R ^{1 is} a different alkenyl radical. The composition also contains a minor amount of the corresponding succinamide and the total nitrogen-containing succinic acid derivative content of the composition is about 58% by weight. The composition also contains about 23% by weight of unreacted polyisobutene with the remainder being pale oil. The nitrogen-containing dispersant in the composition has an approximate molecular weight of about 5000 and the total sample contains 1.4 to 1.8 weight percent nitrogen.

91.1 g of the commercially available succinimide composition described and 140 g of benzene were mixed together until a. Solution had formed, and then the solution became heated to 40 C. To the heated benzene solution of the dispersant were then added at a constant rate to 49 g of the complex calcium methyl cellosolve carbonate added, the 7.3 wt .-% calcium and 7.9 wt .-% bound C0 "contained. Simultaneously with the addition of the complex, 4.5 g of an azeotrope containing 53.5% by weight of water were produced and in which the remainder consisted of methyl cellosolve, added. The complex and the azeotrope were both slowly going over one Added for a period of 35 minutes.

After the addition of the complex and the azeotrope, the solvents were removed from the reaction mixture by slowly heated the mixture to a temperature of 150.degree

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and then after reaching that temperature, mixing with carbon dioxide for about 20 minutes stripped off. The end product that remained after the solvent had been removed was very cloudy and contained gel particles and was considered unsuitable as a lubricating oil additive ..

Example 2

91.1 g of the commercially available used in Example 1 Succinimide dispersant compositions were mixed with 25 grams of benzene and 100 grams of isopropyl alcohol in a 1 liter flask. The mixture was stirred until a homogeneous mixture with the appearance of an emulsion was formed. then the mixture was heated to 40 C and it was with the addition of 49 g of the highly basic complex used in Example 1 (overbasing complex) simultaneously with the addition of 6.5 g of the water / alcohol azeotrope used in Example 1 started. This amount of azeotrope meant an addition of 2.1 moles Water per mole of calcium in the highly basicizing complex. The addition of the complex and the azeotrope were simultaneous carried out over a period of 35 minutes. During the last 15 minutes of adding the complex and the azeotrope the mixture was heated to 55 ° C to maintain its fluidity. After the addition was complete, the solvents were removed therefrom by adding the reaction mixture 150 C and after reaching this temperature over a period of about 20 minutes carbon dioxide through the Mixture headed. The final product formed upon completion of the solvent removal was light, clear and liquid. It was in Soluble in aromatics, but in other hydrocarbon materials only partially soluble. Therefore, when mixed into a light-colored mineral oil, the mixture became somewhat cloudy and the composition thus obtained was not optimal for additional purposes.

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The above Examples 1 and 2 pulled that through Use of a dispersant diluent consisting of a mixture of isopropyl alcohol and benzene, an acceptable product can be made, however the use of benzene alone does not lead to a satisfactory product.

Example 3

The materials and procedures used in Example 2 were used in a further experiment. used, but this time 50 g of benzene were used in the starting mixture instead of 25 g. The educated highly basic product showed improved compatibility with base oils, hexane and naphtha compared to the in Example 2 prepared highly basic product.

Example 4

The materials and procedures used in Examples 2 and 3 were repeated, this time together with 100 g of isopropyl alcohol to produce the solvent system instead of that in Examples 2 and 3 applied smaller amounts of benzene 100 g of benzene were used. The resulting highly basic end product was. bright, clear and liquid and it was completely soluble in all hydrocarbons.

All of the products obtained in Examples 1 to 4 had a base number of about 100, determined by the acetic acid titration method, on.

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Example 5

Another commercially available succinimide composition contains 37% by weight of a succinimide / succinamide mixture which essentially identical to that described in Example 1 is. This commercially available dispersant composition also contains about 12% by weight unreacted Polyisobutene with the remainder consisting essentially of a non-volatile carrier oil. The one containing nitrogen Dispersant has an average molecular weight of about 5500. The nitrogen content of the composition, such as it is placed on the market between about 1.04 and 1.06 weight percent.

205 grams of the described succinimide dispersant composition was mixed with 375 grams of methyl cellosolve. the Mixture was then heated to 38 C and it was with the simultaneous addition of a magnesium alkylate carbonate complex and an azeotrope of the general type described above. The metal complex contained 5.64% by weight of magnesium and was slowly added to the mixture in an amount of 86 g. The addition of the complex took 173 minutes. 23.4 grams of the azeotrope were added over 162 minutes. The azeotrope contained 53.6% by weight of water, the remainder consisted of methyl cellosolve.

After the simultaneous addition of the complex and the azeotrope was complete, solvent removal was started by slowly heating the reaction mixture to 150 C. After this temperature was reached, the Passing carbon dioxide through the mixture and this became

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continued for about 15 minutes. In the process described, 222 g of a bright, clear, viscous liquid. The highly basic dispersion product had a base number of 100.

Example 6

To 205 grams of the commercially available succinimide dispersant composition described in Example 5 was added 375 ml of anhydrous methanol. To the mixture, 75 ml of methyl cellosolve was added to improve its homogeneity. The mixture was then heated to 45 ° C. At this point, the addition of a magnesium alkylate carbonate complex was started at the same time as the addition of a water / methyl cellosolve azeotrope. In addition, 86.7 g of the complex containing 5.64% by weight of magnesium were added over a period of 60.5 minutes, the addition taking place slowly below the surface of the dispersant mixture. 20.3 g of the azeotrope '■', ... containing 53.6% by weight of water (corresponding to a molar ratio of water to magnesium in the complex of 3: 1) were added to the surface of the dispersant mixture over a period of 55 minutes. '. ...! ~ "' -.:·■··;''"'. . . . admitted. After the addition of the complex and the azeotrope had ended, the reaction mixture was distilled up to a flask temperature of 150.degree. The introduction of carbon dioxide was then started and continued for 15 minutes to remove the light end / from the mixture. A light, clear product with an acetic acid base number of about 100 and a BSW value (bottom sediment and water value) of 0.4% by weight would be formed.

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Example 7

205 g of the commercially available ones described in Examples 5 and 6 Succinimide compositions were placed in a 1 liter three neck flask and 375 ml of methyl cellosolve was added to the dispersant. After homogenizing the temperature of the mixture was raised to 38 G and it became high-basic mesh with the simultaneous addition of the complex (overbasing) and the water-containing azeotrope started. The complex was a magnesium alkoxide carbonate complex with 5.64 wt% magnesium. 86.7 g of this complex were added over a period of 177 minutes added to the dispersant mixture. The reaction mixture was admixed with 15.3 grams over a period of 164 minutes of the azeotrope containing 47.3% by weight of water (corresponding to a molar ratio of water to magnesium of 2: i) was added. After completion of the addition of the complex and the azeotrope, the volatile solvents were distilled off from the mixture, until a piston temperature of 150 ° C has been reached. The mixture then became carbon dioxide for 15 minutes directed. In this way, 225 g of a clear, pale product with an acetic acid base number of about 100 and were obtained a B.S. & W. value of 0.2% by weight.

Example 8

205 g of the commercially available succinimide dispersant described in Examples 5 to 7 were added together with 375 ml Methyl cellosolve introduced into a reaction flask. The mixture was heated to 45 C and it was added with the addition a magnesium-containing carbonate complex and a water containing azeotrope started. 86.7 g of the complex, which contained 5.64 wt% magnesium, were over a period of

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80 minutes were added and, over a period of 72 minutes, 13.5 g of the azeotrope containing 53.6% by weight of water were added (Molar ratio of water to magnesium = 2: 1) was added. Upon completion of the addition of the complex, the volatile solvents became removed in the manner described in Example 6 and 226.5 g of a clear and light product were obtained a B.S. & W. value of 0.3% by weight.

Example 9

For the preparation of a dispersant composition made highly basic with magnesium carbonate in the manner indicated below a commercially available succinimide composition of the type described in Example 5 was used. 138.8 g of the commercially available Succinimide composition, 250 ml of benzene and 50 ml of methyl cellosolve were mixed together in a reaction flask and heated to a temperature between 40 and 45 C. At this temperature, 42.8 g of a magnesium alkylate carbonate complex were simultaneously produced with 7.62 wt .-% magnesium and 14 ml of a 53.6 wt .-% water containing and the remainder Add methyl cellosolve existing azeotrope to the reaction flask over a period of 25 minutes. The one added to the azeotrope Water was equivalent to 3 moles per mole of magnesium added with the complex. After completing the addition of the complex and the azeotrope to the reaction mixture, 25 ml of methyl cellosolve were used to rinse out the addition funnel and put in added to the reaction mixture during the rinsing process. Distillation was then started to remove the solvents and this was carried out over a period of 45 minutes. At this point the temperature of the mixture was 150 ° C and the mixture was bright and clear. The final light fractions of the mixture were then added over a period of 15 minutes

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Stripped of carbon dioxide. According to this procedure, one obtained 150 g of a light-colored, fairly flowable (fluid) product with a base number of 103. ·

Example 10

69.4 g of the commercially available succinimide dispersant composition used as starting material in Examples 1 to 4 were mixed with 69.4 g of pale oil having a viscosity of 170 SiSU at 210 ° C and the diluted dispersant composition was in a reaction flask with 250 ml of benzene and 50 ml of methyl cellosolve introduced. The mixture was heated to a temperature of 40 to 45 ° C., at which point the addition of the magnesium-containing complex described in Example 9 and the water azeotrope was started. Over a period of 10 minutes, 20.5 ml of the magnesium coraplex and 7 ml of the azeotrope were added simultaneously. The dropping funnel used to add the complex was then rinsed with 3.0 ml of methyl cellosolve. After completion of the addition of the complex and the azeotrope was started Destil lation and this was continued for 50 Läng-minutes, during which time the temperature of the reaction mixture was gradually raised to 150 ⁰ C. Carbon dioxide stripping of the final light fractions was then started and continued for 15 minutes. Upon completion of stripping, 143.7 was obtained. g of a light, flowable, highly viscous dispersion product with a base number of 74.

. free play H

172 grams of the commercial succinimide dispersant composition described in Example 5 were together with 250 ml of benzene and 50 ml of methyl cellosolve in a three-necked reaction

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piston given. After mixing the materials in the flask - the mixture was brought to a temperature between 40 and 45 ° C heated. Then 92.5 g of a calcium alkylate carbonate complex were added to the mixture with 7.29% by weight calcium together with 12.3 ml of a water / methyl cellosolve azeotrope containing 53.6% by weight water admitted. The addition of the complex was complete within 30 minutes and the addition of the azeotrope was within ν finished in 35 minutes. After about 3/4 of the complex was added to the mixture, the mixture turned weak cloudy and they. remained cloudy until the addition of the complex was complete. At this point the mixture was at for 30 minutes 83 C and refluxed by refluxing the mixture became light and fluid. Then distillation was used to remove the volatile solvents started and this was continued for 45 minutes until the temperature of the mixture reached 150 ° C. The mix was then stripped with carbon dioxide for 30 minutes. This produced 190 g of a light-colored, flowable product with a base number of 100 received.

Example 12

172 g of another commercially available ash-free, nitrogen-containing one A dispersant composition having an average molecular weight of about 9,000 was made with 250 ml of benzene and 200 ml of isopropyl alcohol mixed in a reaction flask and the mixture was heated to a temperature between 40 and 45 ° C. After this temperature was reached, 92.5 g of a calcium alkylate carbonate complex containing 7.29% by weight calcium, simultaneously with 12.2 ml of one containing 53.6% by weight water Added water / methyl cellosolve azeotrope to reaction flask. The addition of the complex and the azeotrope was

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- 27 - finished after 35 minutes.

It was then used to remove the solvent from the mixture distillation was started and continued for one hour during which time the temperature was gradual was increased to 84 C. At this point, 350 ml of solvent had drained overhead and the reaction mixture was in the piston had become very viscous and it had a tendency to separate into two phases. 250 ml Given η-hexane and the distillation was started again. At 95 ° G the flowability of the mixture was in the flask improved and the distillation was continued until a flask temperature of 150 ° C was reached. Then were 200 ml of n-fteptane are added to the flask to make a gel-like Wash emulsion down, covering the top of the flask covered and this added heptane was removed by distillation. Finally, 200 ml was added to the reaction mixture Benzene and 100 ml of isopropanol were added and the distillation was continued to bring the temperature of the reaction mixture up .190 C to increase. At this point the distillation was stopped. 195.4 g of a product were obtained which fell through Light was pretty bright.

Example 13

1720 grams of the commercial succinimide dispersant composition described in Example 5 were crumbled with 1888 g (2147 ml) of benzene and 1888 g (2407 ml) of isopropyl alcohol in a 12 liter reaction flask mixed. The contents of the flask was heated to a temperature between 40 and 45 C. Then they were simultaneously at a constant rate 925.1 g of a calcium alkylate carbonate complex (with 7.3 wt .- ^

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Calcium and 8.44 wt% carbon dioxide) and 122.7 g of one 53.4 wt.% Water containing water / methyl cellosolve azeotrope was added to the flask. The azeotrope was over added over a period of 30 minutes and the complex addition was completed within 35 minutes. Then became the temperature of the reaction mixture slowly increased to 150 ° C. over a period of three hours. The product was stripped with carbon dioxide for an hour. In this way, 1881 g of a light, flowable material were obtained Product.

To prepare an amount of this product sufficient to run an engine test, the above was used A method of basifying the succinimide dispersant composition using the calcium complex Repeated until a total of 11025 g of product had been obtained. The ones obtained in the various rounds combined products had a base number of 102.

Example 14

In an engine test to investigate those produced according to the invention The highly basic calcium succinimide dispersion prepared as in Example 13 became the highly basic dispersant composition to a solvent-refined paraffinic base oil of the type Mid-Continent S.A.E. 30 added. The dispersant additive constituted 10% by weight of the thus prepared lubricating oil composition and the composition also contained 1% by weight zinc dithiophosphate as an oxidation inhibitor. The lubricating oil composition was then tested in a diesel test engine under Caterpillar 1-H conditions. The test lasted 240 hours and the examined

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Lubricating oil composition passed this test. The volume percentage the head groove of the piston, which was filled with varnish deposits at the end of the test 1.2. The lower grooves were clean. A slight deposit of varnish was found on the first piece, the however, the remaining parts and the underside of the piston were clean.

Example 15

860 g of the commercial succinimide dispersant composition described in Example 5, 86Og Pale Oil 100, 2500 ml benzene and 2000 ml isopropanol were in a flask mixed together and heated to a temperature between 40 and 45 C. 1185 g of a calcium alkylate carbonate complex with 7.29 wt% calcium and 314 ml of an azeotrope containing 53.6 wt% water were added over a period of time of 35 and 30 minutes respectively added to the mixture at the same time. After completion of the addition of the complex were A further 157 ml of the azeotrope were added over a period of 10 minutes. The solvents were left over for a period of time from 2 hours and 20 minutes to a bulb temperature distilled off from 150 C. The product was stripped with carbon dioxide for one hour and after stripping 1952 g of a light-colored, flowable, highly basic dispersion were obtained.

Another batch of the highly basic calcium dispersion described above was prepared, this time instead of by Pale Oil 100, Pale Oil 170 was used. These The batch of dispersion contained 940 g of product. Then the same procedure was used to make more

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939 g of product and these three product batches were run an engine test raii. united in one another. The United Products from the three runs had an acetic acid base number of 151.

The thus-prepared, highly basic made with calcium Succinimiddi ^c persion was added to a solvent refined paraffinic base oil from the Mid-Continent SAE-30-type to achieve a 8 wt .-% dispersion in the base oil. The lubricating oil composition so prepared also contained 1.05% by weight of zinc dithiophosphate as an antioxidant. The lubricating oil composition was tested and evaluated using a standard Ford engine of 4750 cm (289 cubic inches) in accordance with a standard MS Sequence VB internal combustion engine test. According to the industry-recognized standard rating used in this test, the varnish build-up on the piston is rated from the numbers 1 to 10, with the number 10 indicating a clean piston which is characteristic of a new engine. The highly basic lubricating oil composition containing the succinimide dispersion made highly basic with calcium and produced by the process according to the invention had a piston varnish value of 8.

Another criterion that is used in the standard engine test is the evaluation based on the total amount of varnish (related on the total accumulation of the varnish on various parts of the engine examined). The scale used here works from 1 to 50, where 50 means completely clean. The lubricating oil composition tested had a value of 46.9. In the end the total amount of the enriched sludge was determined and the result was a rating of 39.1, again based

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BATH

on a scale from 1 to 50, with 50 indicating a clean engine without any dirt deposits. The tested lubricating oil composition was slightly better than required by the currently valid industry standard values.

Example 16

205 g of a commercially available ashless nitrogen-containing dispersant composition was added to 375 ml Methylcellosolve in one with a stirrer, a thermometer and a reaction flask fitted with a reflux condenser and heated to 38G. The dispersant acted it is one made by the procedures described in Example 1 of US Pat. No. 3,338,831 using polyisobutylene having a molecular weight of 2,000 to prepare the polyisobutenyl succinic anhydride and using a molar ratio of this succinic anhydride to the amine of 1: 1 in the preparation of the acylated nitrogen containing dispersant. The concentration of the dispersant in the non-volatile carrier oil in the starting composition was 55% by weight and contained the composition 0.9 wt% nitrogen and had a total base number of 13 on.

To the heated mixture of dispersant composition and methyl cellosolve was then added simultaneously 86.7 grams of one Magnesium alkoxide carbonate complex (with 5.64% by weight magnesium) and 20.3 g of a water / methyl cellosolve azeotrope (with 53.6% by weight) was added. With this addition the complex was below the stirrer over a period of 172 minutes added and the azeotrope became over a period of time

309812/1193.

introduced onto the surface of the reaction mixture for 158 minutes. After the addition of the complex and the azeotrope had ended, the mixture was distilled to a bottom fraction temperature (flask temperature) of 150.degree. During the distillation the mixture became very thick and viscous between 70 and 80 ° C. Then it started to get thinner and less viscous at 100 ° C. After the distillation, the mixture was stripped _{with CO 9.} 223.2 g of a light, flowable product with a BS&W value of 0.4% by weight were formed.

Example 17

In this example, an ashless, nitrogen-containing dispersant composition was used which was prepared according to was prepared by the process described in Example 1 of U.S. Patent 3,338,831. That to manufacture polyisobutylene used in the dispersant composition had a. Molecular weight of 1100 and that in the process applied molar ratio of polyisobutenyl succinic anhydride to amine was 2: 1. The concentration of the dispersant in a non-volatile carrier oil (Pale Oil 100) in the starting composition was 50% by weight and the dispersant composition contained 1.4 wt% nitrogen and had a total base number of 11. The in The basification procedure described in Example 16 was carried out using methyl cellosolve and the like, magnesium-containing complex and des the same azeotrope in the same weight ratio as described in this example. In this experiment, that was However, azeotrope was added to the reaction mixture over a period of 166 minutes and the complex was added over a

309812/1 193

Added for a period of 179 minutes. During heating and after distillation the reaction mixture remained quite thin and after the nitrogen stripping was stopped 222.3 g of a light-colored, flowable product remained. The product had a B.S. & W. value of 0.2% by weight.

Example 18

375 ml of methyl cellosolve were in a reaction flask with 205 grams of an ashless nitrogen containing dispersant composition mixed prepared as described in Example 1 of U.S. Patent 3,367,864. The polyisobutylene used for the preparation had a molecular weight of 1,100 and that for the preparation of the dispersant applied molar ratio of succinic anhydride to tetraethylene pentamine was 2: 1. Then it became Succinimide reacted in a molar ratio of 1: 1 with propane sultone. The dispersant composition contained 50% by weight of a non-volatile carrier oil, 1.1% by weight Nitrogen and 1 wt% sulfur. It had a total base of 14 and a total acid number of 10.

The mixture of the methyl cellosolve and the dispersant composition was heated to 38 C before the addition of the magnesium complex and the azeotrope. The one used Magnesium complex and the azeotrope used were the same as indicated in Example 16 and they were added simultaneously to the reaction mixture over a period of 150 and 157 minutes, respectively. Then the distillation was started and this was up to a piston temperature (bottom fraction temperature) continued from 150 C. The mixture was then

stripped with carbon dioxide to give 222 g of one

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ίί

light, flowable product with a B.S. & W. value of 0.2 wt%. . ■

Example 19

In the highly basic method used here, a dispersant composition was used which, as described in Example 18, this time the polyisobutylene starting material having a molecular weight of 2000 and had succinic anhydride with the tetraethylene pentamine compound in a molar ratio of 1: 1 was implemented. Then the succinimide obtained was reacted with propane sultone in a ratio of 1: 1 and the product contained 0.6 wt% nitrogen and 1.1 wt% Sulfur. Its base number was 9. A 50% by weight solution of the ashless dispersant and the oil was then added the method described in the case of games 6 to 18 for Subjected to high basicization, this time adding the azeotrope to the reaction mixture over a period of 160 minutes and the addition of the complex to the reaction mixture was carried out over a period of 177 minutes became. In this case, after completion of the CO 2 stripping, one obtained a small amount of translucent gel on the side walls of the reaction flask and the clear product was relatively viscous. The product had a B.S. & W, value of 1.0% by weight.

Example 20

As described in U.S. Patent 3,172,892, a Succinimide dispersant composition made using polyisobutylene having a molecular weight of 1000 as a starting material and with implementation of the obtained

309812/1193

Succinic anhydride with letraethylene pentamine in one 2: 1 molar ratio to form the imide. The dispersant composition, which was subjected to a highly basic process contained 85% by weight of the same Succinimide Dispersant in Pale OiIv The dispersant composition contained 2% by weight nitrogen and had a total base number of 42. 375 ml of methyl cellosolve were in the dispersant composition was added to a reaction flask and the mixture was heated to 38 ° C. At this Temperature was on the walls of the reaction flask, which limit the vapor space above the reaction mixture, some condensate accumulated. At this point in time, the reaction mixture was fairly thin and homogeneous. Then were the azeotrope described in Example 16 and the magnesium complex were added simultaneously to the reaction mixture. The azeotrope was added over 156 minutes and the complex was added over 176 minutes admitted. After about 80 minutes of simultaneous addition, the reaction mixture became inhomogeneous and remained during the Completion of the addition of the azeotrope and the complex and inhomogeneous during the distillation until a flask temperature (Bottom fraction temperature) of 80 C was reached. Then the reaction mixture became homogeneous again. After completion of the stripping with carbon dioxide, 225 g of one was obtained viscous product with a B.S. & W. value of 0.05% by weight.

Example 21

A succinimide composition prepared as described in Example 10, however, a molar ratio in their preparation of succinic anhydride to amine of?: 1.2 was applied and 66% by weight of the succinimide dispersant in oil was used

^309812/1193

was mixed with 375 ml of methyl cellosolve and that High base procedures were then performed as described in Example 20. The time of the addition of the azeotrope was 165 minutes and the magnesium complex was added over a period of 180 minutes. Also here was the mixture was initially inhomogeneous, then homogeneous again when the temperature reached 80 ° C. during the distillation. Man received 225.6 g of a viscous product with a B.S. & W. value of 0.05% by weight.

In the foregoing, the invention has been made more preferred in terms of certain ones Embodiments explained in more detail, it is clear to the person skilled in the art, however, that these with regard to the starting materials and the process conditions can be varied and modified without falling outside the scope of the present invention Invention is abandoned.

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Claims (21)

Claims. 1. A process for the preparation of a stable dispersion of an inorganic metal compound in a metal-free, oil-soluble, ash-free dispersant compound which contains acylated nitrogen, characterized in that a mixture comprising (a) about 10 to about 60% by weight of a non- volatile, oil-soluble carrier material with a boiling point above about 150 ° C. and (b) about 90 to about 40% by weight of a metal-free, acylated nitrogen-containing ash-free, oil-soluble dispersant compound with an organic solvent from the group of monohydroxy alcohols with 1 to 4 carbon atoms and the mixtures of such alcohols with monocyclic aromatic hydrocarbons, the alcohol / aromatic mixture containing at least 25% by weight of one or more of these alcohols, in a weight ratio of organic solvent to the mixture of the oil-soluble carrier material and the dispersant compound of at least 1, 25: 1 mixes, the mixture of the organic solvent, the non-volatile carrier material and the dispersant compound heated to a temperature of about 25 to about 100 G, to the heated mixture of the solvent, the oil-soluble Carrier material and the dispersant compound about 5 to about 35 wt .-% of a metal alkoxide carbonate complex with calcium, magnesium or barium as the metal component, while the temperature of the mixture is between about 25 and about 100 C, with the addition of the complex in the presence of such an amount of water in the mixture of the solvent, the oil-soluble carrier and the dispersant 3 0 9 8 12/1193 Completed agent compound, which exceeds the stoichiometrically required amount for hydrolyzing the metal alkylate carbonate complex and is about 0.5 to about 6.0 % by weight, based on the total weight of the mixture including the water and the complex, and from the reaction mixture to which the complex has been added, at least all under
volatile materials removed. den is at least all those boiling below about 125 C. 2. The method according to claim 1, characterized in that a metal-free, acylated nitrogen-containing, oil-soluble, ashless dispersant compound having a molecular weight from about 4000 to about 10,000 from the group of the imides, amides and esters is used, which are obtained by reacting a Alkenyl carboxylic acid or an alkenyl carboxylic acid anhydride with a nitrogen-containing organic compound having at least one amino or hydroxy group are. 3. The method according to claim 1 and / or 2, characterized in that a complex of the general formula is used M ^ OCH ₂ CH ₂ OR) ^^ OC-OCH ₂ CH ₂ OR) _x in the M a bivalent metal ion from the group calcium, Magnesium and barium and R is an alkyl group having 1 to 6 carbon atoms or an organic radical of the formula HH
-CCOR ¹ Il H H - ■ - ■ - 309812/119 3 wherein R ¹ denotes an alkyl group having 1 to 4 carbon atoms, and χ denotes a number from 0.5 to 1.5, preferably from 0.75 to 1.0, which contains about 5 to about 8% by weight of metal. 4. The method according to at least one of claims 1 to 3, characterized in that the mixture of organic solvent and dispersant is water in an amount from about 1.5 to about 4 moles per mole of the complex is added will. 5. Vm driving according to at least one of claims 1 to 4, characterized in that the mixture of the organic solvent and the dispersant is at a temperature heated from about 30 to about 60 C and during the addition of the complex kept within this temperature range will. 6. The method according to at least one of claims 1 to 5, characterized characterized in that the presence of water in the solvent / dispersant mixture is achieved during the addition of the complex by adding to the solvent / dispersant mixture an alcohol / water azeotrope is added simultaneously with the addition of the complex. 7. The method according to at least one of claims 1 to 6, characterized in that there is used as the organic solvent 2- methoxy-1-ethanol. 8. The method according to at least one of claims 1 to 7, characterized in that the volatile material is removed by that it is from the reaction mixture up to a col- 309812/1133 ^: Bent temperature between about 125 and about 10 ° C distilled off and then the light end fractions by passing through stripping of carbon dioxide through the reaction mixture. 9. The method according to at least one of claims 1 to 8, characterized in that a complex is used which contains about 7 to about 8 wt. % Calcium metal, and that the amount of in the solvent / dispersant mixture during the addition of the Complex water present about 1.5 to about 4 moles per mole of the complex added. 10. The method according to at least one of claims 1 to 8, characterized characterized in that one uses a complex that is about 5 to about 6 wt .-% magnesium metal, and that the The amount of water present in the solvent / dispersant mixture during the addition of the complex is about 2 to is about 4 moles per mole of complex added. 11. The method according to at least one of claims 1 to 10, characterized characterized in that a nitrogen-containing dist Pergiermittelverbindungen is used, which is produced by reacting an alkenyl succinic anhydride with a polyamine has been. 12. The method according to at least one of claims 1 to 11, characterized characterized in that a nitrogen-containing dispersant compound is used which has an average Has a molecular weight of from about 5,000 to about 9,000 and consists essentially of succinimide and succinamide compounds consists. 309812/1193 13. The method according to at least one.der claims 1 to 12, characterized characterized in that an organic solvent is used, which about 50 wt .-% of a monohydroxy alcohol with Contains 1 to 4 carbon atoms and about 50% by weight benzene. 14. The method according to at least one of claims 1 to 12, characterized characterized in that an organic solvent is used which contains at least 25% by weight of 2-methoxy-1-ethanol contains that the complex is added in a solution in 2-methoxy-ethanol and that the presence of water is achieved in the solvent / dispersing mixture during the addition of the complex by simultaneously with the addition of the complex of the solvent / dispersant mixture creates an azeotrope of water and 2-methoxy-1-ethanol clogs. 15. The method according to at least one of claims 1 to 8, characterized characterized in that a complex is used which contains from about 7 to about 8% by weight calcium metal, and that the amount of the water present in the solvent / dispersant mixture during the addition of the complex from about 1.6 to is about 2.4 moles. 16. The method according to at least one of claims 1 to 15, characterized characterized in that the solvent used is a mixture which consists essentially of equal parts of isopropanol and benzene. 17. The method according to claim 12, characterized in that a complex of the general formula is used ClH ₂ OR} ^; CO-CC) Cfl ₂ ClI ₂ ÜR) _x 3 0 9 B 1 2/1 1 9 3 in which M is a divalent metal ion from the group consisting of calcium, magnesium and barium and R is an alkyl group with 1 to 6 Carbon atoms or an organic radical of the formula HH
-CCO-R ' HH. . wherein R ¹ denotes an alkyl group having 1 to 4 carbon atoms and χ denotes a number from 0.5 to 1.5, preferably from 0.75 to 1.0, which contains about 5 to about 8% by weight of metal. 18. The method according to claim 16, characterized in that the organic solvent and a dispersant existing mixture heated to a temperature of about 30 to about 60 C and during the addition of the complex at this Temperature is maintained. 19. The method according to claim 17, characterized in that the water of the mixture of the organic solvent and is added to the dispersant in an amount of from about 1.5 to about 4 moles of water per mole of complex. 20. The method according to at least one of claims 1 to 19, characterized characterized in that the volatile material is distilled off from the reaction mixture to a flask temperature of about 150 ° C. and then stripping off the light end fractions of the reaction mixture by passing it through of carbon dioxide is obtained through the reaction mixture. 21. The method according to claim 19, characterized in that the 3 IHHU 2 / M S 3 Presence of water in the solvent / dispersant mixture is achieved during the addition of the complex by simultaneously with the addition of the Complex an alcohol / water azeotrope to the solvent / dispersant mixture admits. 309812 / 119.3