DE1245010B - Process for the production of stable dispersions of carbonates of the alkali and alkaline earth metals, with the exception of magnesium in lubricating oils - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

245 010 t 6 9/0 0 A 1 0

Int. CL: ClOm

•O.

German KL: 23 c-1/01

File number: C 16924 IV c / 23 c
Filing date: May 30, 1958
Opened on: July 20, 1967

It is well known that in addition to lubricity, durability, etc., high-performance lubricating oils must Possess properties to disperse insoluble substances, which as combustion residues in the engine stay behind and also neutralize acidic, resin-like compounds that can either by the oxidation of the oil or by the interaction of the oil with the fuel combustion formed acids of sulfur or through both processes.

The production of lubricating oil additives with a base reserve has so far been carried out in such a way that an oil-soluble, anionic dispersant, e.g. B. a metal sulfonate, added to the lubricating oil and subsequently reacted with an inorganic base or a metal carbonate. It Oil-soluble basic salts or mixed salts of the sulfonic acid used or analogously are formed in the process built adducts. Another way to make such lubricant additives has been by dispersed the aqueous solution of an inorganic compound in the oil by means of a dispersing agent and then the solvent evaporated.

However, the lubricating oils produced by these processes have major disadvantages. On the one hand is their base reserve is very small, on the other hand the dispersed solids have too large a particle diameter. Both circumstances have a detrimental effect on the service life of an internal combustion engine the end. A base reserve that is too low does not guarantee adequate protection against the corrosive Influences of acidic combustion products, while too large a particle diameter of the dispersed particles cause additional wear on the sliding parts of the engine.

These disadvantages do not have lubricating oils which have been produced by a process that thereby is characterized in that a known manner from alcohols having 1 to 5 carbon atoms and a basic alkali or alkaline earth compound - with the exception of magnesium - by introducing The salt obtained from carbon dioxide is dispersed in the lubricating oil by means of known dispersants and then the dispersion obtained is heated to an elevated temperature of about 150 to 160 ° C, to remove the solvents and water.

The salt obtained when introducing carbon dioxide has the following formula:

M (- O - C - O - R) _x

Process for the production of stable dispersions
of carbonates of the alkali and alkaline earth metals - with the exception of magnesium - in lubricating oils

Applicant:

Continental OiI Company,

Ponca City, Okia. (V. St. A.)

Representative:

Dr. W. Germershausen, patent attorney,

Frankfurt / M., Gärtnerweg 28

Named as inventor:

Robert Lewis Carlyle, Lake Jackson, Tex .;

Earl Frederick Morris,

Ponca City, Okia. (V. St. A.)

wherein

M = a metal from the group of alkali and alkaline earth metals, preferably sodium.
Is barium or calcium,

x = the valence of M,

R = a lower alkyl group.

When this metal salt is heated in the presence of moisture, oil-insoluble metal carbonate is produced in extremely fine dispersion. Sodium, barium and calcium oxides and hydroxides and their hydrates can be used as alkali or alkaline earth compounds. Other suitable inorganic compounds are the sodium, barium and calcium salts of acids, the dissociation constant is less than 1 x 10 ~ ⁷ z. B. boric acid, carbonic acid, carbolic acid and thiocarboxylic acid.

Mineral, vegetable, animal and synthetic oils can be used as lubricating oils.

The oils can be used to reduce the viscosity with inert solvents, e.g. B. petroleum naphtha or Hydrocarbons are diluted. The dispersants can be ionic or non-ionic Dispersants, e.g. B. sulfonates, phenols,

organic phosphorus compounds, olefins treated with phosphorus sulphide and metal soaps of carboxylic acids be used.

704 617 / 4S4

In the following illustrative examples of the method, the parts indicated are Parts by weight. The value given in front of the cylinder oil is the SSU value at 37.8 ° C.

example 1

A suspension of 5 parts of calcium oxide (85% active CaO) in 80 parts of methanol was used a water content of 1% and carbon dioxide blown through this suspension until the heat of reaction had subsided. The product was filtered off and 33 parts of a solid, water-soluble, unstable connection gained. When left standing, this compound slowly decomposes and is released of carbon dioxide, whereby calcium carbonate is formed.

95 parts of the compound became a 50% solution of neutral calcium postdodecylbenzenesulfonate added in 170 cylinder oil. (Postdodecylbenzene is a distillation overrun resulting from the manufacture of dodecylbenzene, consisting of one Mixture of mono- or dialkylbenzene in a molar ratio of 2: 3). The mixture was stirred to obtain the To suspend calcium salt, and then heated to 150 ° C to decompose it and distill off the methanol. The fine dispersion obtained was clear and miscible with oils. Their base number was 86.

A similar product is obtained when a calcium salt as shown above becomes 50% Solution of neutral barium postdodecylbenzenesulfonates is added.

Example 2

Through a suspension of 8.25 parts of calcium oxide in 130 parts of methanol having a water content of I ⁰ Zo carbon dioxide was bubbled, keeping the temperature was maintained at about 25 ° C. The suspension obtained was filtered and a suspension made up in 92.5 parts of a solution of postdodecylbenzenesulfonic acid in 170-cylinder oil. The suspension was heated to 150 ° C. in order to replace the calcium and to distill off methanol. The product was mixed with filter aids and filtered to give a transparent, oil-miscible fine dispersion with a base number of 88.

Example 3

In 100 parts of a solution obtained by dissolving 25.8 parts of barium oxide in 120 parts of methanol with a water content of 1%> carbon dioxide was introduced until the heat of reaction had subsided. The forming The white barium salt was filtered off. 50 parts of this barium salt became 155 parts of a 50% strength Added solution of barium postdodecylbenzenesulfonate in 170 cylinder oil. The mixture was Stirred vigorously and quickly heated to 150 ° C to decompose the barium salt and distill off the methanol. The product was centrifuged and gave a clear, oil-miscible fine dispersion with a base number of 57.

Example 4

6.4 parts of calcium hydroxide were suspended in 80 parts of isopropanol and carbon dioxide was suspended for 2 hours initiated. The obtained calcium salt was filtered to give 95 parts of a 50% solution of Calcium postdodecylbenzenesulfonate in 170 cylinder oil was added and heated to 150 ° C. After filtering a clear, pale product with a base number of 82 was obtained by filter aid.

Example 5

33 parts of the solid ίο calcium-carbon dioxide-methanol compound prepared according to Example 1 were to a solution of 50 parts of polyoxyethylene sorbitol 4,5 oleate added in 80 parts of 170 cylinder oil. The mixture was vigorously stirred and expanded Heated to 150 ° C to decompose the calcium salt and to distill off the methanol. The product obtained was centrifuged, whereupon a clear, oil-miscible fine dispersion with a base number of 59 was obtained became.

Example 6

12 parts of calcium hydroxide were suspended in 44.4 parts of methanol. The suspension became vigorous stirred and 36 parts of a 5O% solution of postdodecylbenzenesulfonic acid in 170 cylinder oil and

* 5 38.4 parts of naphtha added. Carbon dioxide was bubbled through the mixture until 13.4 parts of carbon dioxide were added. The reaction mixture was then heated to 150 ° C. to evaporate the solvents and decompose the calcium salt. After filtering, the product has a base number of 190 and contains 7.9% calcium and 3 ⁰ zo sulfur.

Lubricants are prepared by adding 5 parts of a product according to Examples 1 to 7, 9, 12 and 13 to 95 parts of an SAE 30 lubricating oil mixture, which added a small amount, Wax olefin treated with phosphorus pentasulfide. Each of the manufactured according to the above Mixtures are then heated to about 60 ° C with stirring to ensure uniformity To obtain mixture.

The lubricants so produced are tested together with the SAE 30 lubricating oil containing phosphorus pentasulfide treated wax olefin as a control in an internal combustion engine. This test can be briefly described as follows: 4-cylinder petrol engines (light tractor engines from International) run 40 hours at 2500 rev / min to llBrems-PS, at oil temperature of 137.8 ⁰ C.

At the end of the test run, the motors are dismantled and their parts examined. At the same time, an engine using SAE 30 oil containing phosphorus pentasulphide is used as a control containing treated wax olefin. The engines in which lubricants are used which contained the products according to the invention as additives show a lower rate Wear than the engine on which the control lubricant was used.

In short, the experiments have shown that:

1. Base numbers in the range from about 100 to 130 result in products with optimal viscosity,

2. An 8 to 4 per cent use of calcium hydroxide and a 24 per cent use of carbon dioxide are optimal

3. The carbonation treatment should be carried out at a temperature in the range between 26.7 and 32.2 ° C

done to have optimal base number and solubility to achieve,

4. The use of alcohol and metal in a weight ratio above 6: 1 does not offer any obvious advantage.

The procedure of Example 1 was repeated except that the amount of blown carbon dioxide was varied. The results are shown in FIG. 1 summarized, where on the ordinate the Base number and on the abscissa the amount of carbon dioxide is entered. The base number of the product increases rapidly with the amount of carbon dioxide used, up to about 9.07 kg Carbon dioxide on 0.454 kg of metal, thereby increasing the base number with a sharp increase in the number used Amount of carbon dioxide increases very slowly. Fig. 2 shows that the viscosity at a base number between 100 and 130 reaches a minimum. The base number is on the abscissa and the The ordinate shows the viscosity at 98.9 ° C. in SSU units.

Claims (1)

Claim: Process for the production of stable dispersions of carbonates of the alkali and alkaline earth metals, except magnesium, in mineral and synthetic lubricating oils, characterized in that a known Way from alcohol with 1 to 5 carbon atoms and a basic alkali or ίο Alkaline earth compound by introducing carbon dioxide obtained salt is dispersed in the lubricating oil by means of known dispersants and then the dispersion obtained is heated to an elevated temperature of about 150 to 160.degree to remove the solvents and water. Considered publications:
French patent specification No. 1136 852,
ao 1148 986, 1149 566, 1152 926, 1153 138,
139. 1 sheet of drawings 709 tn / 484 7. <7 O Bundejdruckerei Berlin