DE1119270B - Process for the production of oil-soluble basic salts of organic carboxylic or sulfonic acids - Google Patents

Description

GERMAN

PATENT OFFICE

N12130IVb / 12o

REGISTRATION DATE: APRIL 20, 1956

NOTIFICATION OF THE REGISTRATION AND ISSUE OF THE
EDITORIAL: DECEMBER 14, 1961

For many purposes, e.g. B. to improve the cleaning effect in lubricating oils, it is Such oil-soluble polyvalent metal salts of organic carboxylic or sulfonic acids are advantageous as detergents to use, the metal content of which is as high as possible. Such so-called basic salts can by reaction of the acid in question with an excess of a basic compound of the polyvalent Metal, such as an oxide, hydroxide or carbonate. In such basic Salts lies the metal in relation to the theoretically for the displacement of the acidic hydrogen atom of the organic Acid required amount in excess.

However, in order to incorporate a relatively large excess of the polyvalent metal into these salts, special measures are required.

From the Australian patent specification 154 686 a process is known, alkaline earth salts of organic Acids. With a higher basicity. It is made from a solution of an oil-soluble organic Run out of acid or a salt of such an acid. This solution will be an excess an inorganic alkaline earth compound, water and a so-called "promoter" (usually a phenolic Compound) added. The mixture is first heated for some time and then by heating drains. The solution can then be filtered to remove undissolved inorganic substances. The solution can optionally be aftertreated with an acid anhydride, preferably carbon dioxide in order to restore the promoter, which went into salt form in the first reaction Freedom to put. The promoter can then be recovered. You can also start with the Carry out carbon dioxide treatment and only afterwards the filtration.

According to one proposal, basic salts with high metal contents can be obtained in a simpler manner come by a polyvalent metal salt dissolved in a hydrocarbon oil of an organic Carboxylic or sulfonic acid in the presence of at least 2 percent by weight of water, based on the solution of the salt with a polyvalent carbonate formed in situ in the reaction mixture Metal implements.

According to another suggestion, very favorable results are obtained if the implementation of the in carbonate formed in situ in the hydrocarbon oil solution of the organic polyvalent metal salt also a water-miscible, oxygen-containing organic solvent, such as methanol or ethanol, is present.

Method of manufacture
oil-soluble basic salts
organic carboxylic or sulfonic acids

Applicant:

Bataafse Petroleum Maatschappij NV,
The hague

Representative: Dr. K. Schwarzhans, patent attorney,
Munich 19, Romanplatz 9

Claimed priority:
Netherlands of April 22, 1955 (No. 196 688)

Lenze Harstra and Haaike Jan Visser,

Amsterdam, Netherlands),
have been named as inventors

The nature of the basic salts thus obtained is not exactly known. But it is conceivable that extremely fine Particles of the metal carbonate insoluble in oil due to the soluble salt of the organic acid in colloidal suspension or form micelles with this, so that the carbonate then behaves like a broken connection. The basic salts in question are perhaps the easiest to use are described as oil-soluble complex compounds of an oil-soluble salt of an organic Acid with a metal carbonate insoluble in oil.

In addition to the solutions of basic salts of organic carboxylic or sulfonic acids, the reaction mixtures generally also contain solid constituents. Therefor there could be various reasons. First and foremost, that which is insoluble in oil is formed in situ Metal carbonate often does not quantitatively change the salt of the organic acid to form a basic one Added salt. It is also possible that the compounds which are responsible for the formation of the carbonate cannot be quantitatively converted into this.

In general, these solid constituents cannot be sharply separated from the solution, but can a gel-like and sludge-like sediment is deposited, which in addition to the solid matter also still contains solvent and basic salt. A recovery of this in itself very valuable

109 749/580

3 4

Components would be very desirable, but in this boiler the acids are replaced by substances of the

precisely because of the type just described, which will be described in more detail below

settling of the separated sediment on Difficult- be fed through the line 14, partially

opportunities. neutralized. The mixture now passes through

It has now been found that this problem is 5 device 3 in boiler 4, where Ca (OH) ₂ (slaked lime)

can be solved if the reaction is not carried out and methanol is supplied through lines 5 and 6, respectively

separated metal salts which have gone into solution and which are. More Ca (OH) _{2 is} introduced than for

separated solid components of the reaction complete neutralization of the acids required

mixture, optionally with the addition of further new. The mixture now passes through line 7 into

neutralizing agent, with the carbon or sulfonio the boiler, in which CO ₂ through the line9

acids to be used as starting compounds is introduced. The CO ₂ reacts with the

converts the oil-soluble normal metal salts. excess Ca (OH) ₂ with formation of CaCO ₃ ,

Although hydrocarbon oil solutions of those acids absorbed by the calcium _{alkyl salicylate, such as C 14} to C 18 alkyl salicylic acids, are prepared so that a basic calcium alkyl salicylate is formed from carbonates, for example chemically. The _{unabsorbed CO 2} leaves the boiler pure CaCO ₃ , precipitated chalk or double through line 10. The mixture passes through washed chalk, does not react, line 11 has to centrifuge 12, where it is surprisingly clear shown that the in the removed solution of basic calcium alkyl salicylate, which separated solid constituents, is discharged into through line 13, and a carbonate formed in situ is immediately reacted with the acids under carbon dioxide, consisting of unconverted development of dioxide . Ca (OH) ₂ , unabsorbed CaCO ₃ , is assumed to some extent that this particular reactivity is broken down by solvent and a portion of basic calcium on a specific interaction between alkyl salicylates. This sludge, the basic sludge still contained in the reaction sludge, is withdrawn through line 14 and returned to boiler 2 with salts of the polyvalent metals and that in 25, in which CaCO ₃ and Ca (OH) ₂ generated in situ, particularly finely divided excess the alkylsalicylic acids and these partly carbonate based. neutralize wisely.

The new method of operation described here according to FIG. II is a solution of a technical one

Not only can a considerable saving be made on the mixture of C ₁₄ - to Cjg-alkylsalicylic acids in

Achieve required basifying agents, but 30 xylene passed through line 1 into the boiler 2. In

At the same time, the proportion of tech- this boiler is reduced by the acids through the im

nically no longer usable waste materials. the following substances, which are described in more detail, which

In addition, the yield of the basic substances introduced through the line 10 increases in part

see salts of carboxylic or sulfonic acids, which neutralizes. The mixture now passes over the line

are of great importance as lubricating oil additives. 35 device 3 in the boiler 4, where methanolic solutions

The essential technical progress of the new from CuCl ₂ or Ka (OH) through the lines 5

technical teaching in relation to the procedure of or 6 -supplied. It will be sufficient

Australian patent is mostly therein to amounts of these compounds added to more

see that you can form according to the invention with a single CuXOH) ₂ than to neutralize the

Distillation is sufficient at the end of the process, 40 acid is necessary. Part of the excess

which is also only required if one is taking Cu (OH) ₂ from the copper alkyl salicylate

the basic salts in question as lubricating oil- formation of a basic copper alkyl salicylate-

wants to use additives, because doing so the presence. The Gemiseh reaches min through line 7

water. On the other hand, it must be in the centrifuge 8, where it is broken down into a clear

known processes water or methanol already 45 solution of basic copper alkyl salicylate, which by

is continuously discharged from the reaction line 9 during the reaction, -and a sludge,

mixture can be removed, and if the pro-which of unabsorbed Cu (OH) ₂ , NaCL ₁

If you want to regain the motor, you have to add some solvent and a proportion of basic

lent treatment with an acidic copper alkyl salicylate. JThis mud will

Compound, such as carbon dioxide, carried out and discharged 50 through line 10 and into boiler 2

then connected to a second distillation ". returned, in which the Cu (OH) ₂ with the

It is true that in the Australian patent it is reacted under alkylsalicylic acids, and in some cases these are also provided for as new ones, which neutralize in the main reaction. Since the quantities of the prefabricated basic NaCl not reacted with the sludge in the boiler 2 cannot be used again with the alkyl salicylic acid, but 55 acids are reacted and freshly filtered residues are continuously formed in the boiler 4 only for the actual NaCl, increased « I the amount of the main reaction used again during the invented mixture contained table salt continuously,
According to the reaction sludge to neutralize the initial caffeine and sulfonic acids to prevent this amount from being too large. However, the sludge which leaves the centrifuge 8 The actual basification is then discharged through the line 10 by means of 60, carried out from time to time by new carbonates formed in situ, and discharged through the secondary line 11. A minor one

In order to explain the invention in more detail, the proportion of the centrifuge 8 through the line 10

Production of two special basic salts after leaving the sludge can also be done continuously

subtracted from the method according to the invention with reference through the branch line 11 and the rest

described on the drawing. 65 can be returned to boiler 2. Another

According to Fig. 1, a solution of a technically appropriate measure is that one in

Mixture of C ₁₄ - to C ^ -Alkylsaücylsäuren in the line 3 built a filter through which the

Xylene passed through line 1 into boiler 2. NaCl can be removed.

The inventive method can, both be carried out continuously as well as in individual approaches.

Suitable acids are. %. B. Erdöbuffonsäuren or naphthenic acids very well.

The following example provides a more detailed explanation.

example

Feed material, consisting of methanol, slaked lime [Ca (OH) ₂ ] and a solution of organic acid in xylene, was introduced into a reaction vessel of 41 capacity equipped with a stirrer. The organic acid used was a mixture of C ₁₄ to C ₁₈ alkylsalicylic acids which had been obtained by the Kolbe-Schmidt carboxylation of C _{14 to C 18 alkyl phenols.} The mixture still contained about 14% unreacted phenols, which, however, do not interfere with the further reaction. Gaseous carbon dioxide was circulated through the reaction vessel, the CO _{2 used being} continuously replaced by fresh CO ₂ . The reaction product was discharged from the bottom of the reaction vessel at such a rate that the liquid level in the reaction vessel remained at the same height. The reaction product was broken down in a centrifuge into a clear solution of basic calcium alkyl salicylate and a sludge which consisted of CaCO ₃ , Ca (OH) ₂ (together about 30%) and the remainder of solvent and basic calcium alkyl salicylate. This sludge was returned to the process to partially neutralize the organic acid before it entered the reaction vessel. This neutralization, in which the solid matter of the sludge is completely converted and CO ₂ escapes, was carried out at a slightly elevated temperature, namely 50 ° C.

The reaction conditions and the results of the experiment are listed in the table. In The following should be noted in this context.

During the course of experiment A, the sludge separated in the centrifuge was not returned to the process. The sludge separated in test A in the centrifuge was used in test 1 to partially neutralize the organic acid before it entered the reaction vessel. In a similar manner, the sludge separated in test 1 was used to partially neutralize the acids in test 2 and the sludge separated in test 2 was used to partially neutralize the acid in test 3. Experiment A does not actually explain the method according to the invention, but was only carried out to obtain a sludge for experiment 1. The total amount of Ca (OH) ₂ and CaCO ₃ contained in the sludge was about V2 equivalent each time, calculated on the organic acid. The total amount of Ca (OH) ₂ and CaCO ₃ which was used in experiments A, 1 and 2 was thus four equivalents each time. In experiment 3, this total was 4 ¹ As equivalents. This large amount in experiment 3 also explains the higher basicity of the product obtained in this experiment.

The basicity of the product is calculated using the formula

- 1). 100%,

in which M is the number of metal equivalents and E is the number of equivalents of organic acid per 100 g of the product. The phenolic hydroxyl group is not taken into account in determining the equivalents of acid.

Basic salts prepared by the process according to the invention are suitable, for. B. as additives to lubricating oils, as additives to liquid heating or fuels for gasoline engines and diesel engines. They can also be used as drying agents, substances with a biocidal effect, especially for the Fungus control, e.g. B. for wood preservatives, for the production of applied to carrier materials Catalysts, for carrying out catalytic reactions in a homogeneous medium and for production of metal mirrors on solid surfaces, etc.

duration Admitted Mixture ) 1 and Met
Xylene lanol
Methanol Ca (OH) ₂
Number of Vp r WPi 1- Tempe CO ₂ content
in the lot Basicity of
Attempt Mixture of acids Weight Weight Equivalents
Calcium
on V CX TtVU
time in
Pp ₃ V rature
in the Reak
tion vessel circulate
the gas on
taken of
Product attempt
No. XyIc
Acids percent percent organic JvCaK.-
functional
vessel in volume CO ₂
in grams
per gram in hours Weight 26.7 33.6 Acids in in ⁰ C percent equivalent to in ° / o 29 percent 26.7 33.6 4th Minutes 30th 90 acid 213 A. 26th 39.7 26.7 33.6 3V ₂ 60 30th 84 55 215 1 24 39.7 26.7 33.6 3V ₂ 60 30th 81 55 213 2 23 39.7 4th 60 30th 74 55 295 3 39.7 60 55

Claims (1)

PATENT CLAIM: Process for the production of oil-soluble basic metal salts of organic carboxylic or sulfonic acids by reacting the metal salts of the named dissolved in a hydrocarbon oil organic acids with a metal carbonate only formed in the reaction mixture and separation the metal salts which did not go into solution during the reaction, characterized in that that these separated solid constituents of the reaction mixture, optionally with addition further neutralizing agents, with the above-mentioned organic acids to the than 7 8 Starting compounds to be used oil-dissolving USA.-Patent No. 2,617,049; borrowed normal metal salts. British Patent No. 786167. Publications Considered: Older Patents Considered: Australian Patent No. 154,686; 5 German Patent No. 1086 701. 1 sheet of drawings © 109 749/580 12.61