DE865339C - Lubricating oils - Google Patents

Description

Lubricating oils It has been found that oil-soluble zinc salts of carboxylic acids with at least 5 carbon atoms in the molecule the properties of mineral or synthetically produced lubricating oils improve significantly when they are used at the same time with oil-soluble reaction products of phosphorus pentasulfide with organic hydroxyl compounds be used.

Acids that are suitable for the preparation of the salts are, for. B. Capric, lauric, palmitic, stearic, montanic, naphthenic or abietic acid as well also acid mixtures that result from the oxidation of petroleum fractions or paraffin Petroleum, brown coal or obtained by converting carbon oxide with hydrogen may be, were made. Suitable acid mixtures can also be obtained if one higher branched alcohols, which are formed in the isobutyl alcohol synthesis, treated with alkali at elevated temperature under pressure. Also unsaturated acids, such as oleic acid and sperm oil fatty acid, as well as acids treated with halogen or sulfur were e.g. B. mono- or dichlorostearic acid or stearic acid, which at x8o to 200 ° has been treated with 8 to ro% sulfur, give suitable zinc salts.

The salts are made in the usual way from the free carboxylic acids produced by the action of zinc, zinc oxide, zinc hydroxide or zinc carbonate. However, one can also start from the alkali metal salts of the carboxylic acids and use them with Convert zinc chloride or zinc sulfate. Part of the zinc can be replaced by barium, Strontium, calcium, magnesium, aluminum, lead or tin or by organic bases, such as butylamine, stearylamine or polyethyleneimine, be replaced. However, the zinc content should generally not be less than 50 mol percent.

Mixtures can also be used in the preparation of the zinc carboxylic acid salts start from carboxylic acids with alkylphenol sulfides or their esters. In this case is at such high temperatures, e.g. B. at zoo up to 300 °, worked and so much Zinc oxide, hydroxide or carbonate applied that the carboxyl groups of the carboxylic acids and the free hydroxyl groups of the alkylphenol sulfides or their esters with the zinc compound can react.

The salts can be prepared, for example, as follows:, * i. x kg of sperm oil fatty acid is heated with = 8o g zinc hydroxide to = 3o to 18o °. That The reaction product is mixed with 2 kg of motor oil in the heat and centrifuged freed from undissolved parts. The ash content of the resulting product is 6 ° / o.

2, i kg of sperm oil fatty acid and i kg of xylenol sulfide (or x, a kg isobntylphenölsulfid) are with 320 g of zinc hydroxide i hour with stirring to 14.o to = 80 ° and then briefly warmed to 23o °, the hot reaction mixture is q. kg of motor oil mixed and centrifuged hot. A viscous product with an ash content is obtained from q. %.

3. 1 kg of stearic acid is heated to 200 ° with 180 g of zinc oxide while stirring, then mixed with 5 kg of motor oil and, after cooling to 50 °, 10 kg of benzene are added. The solution is filtered while warm and freed from benzene by distillation. A paste-like mass with an ash content of 2% is obtained. -q .. 1 kg of a mixture of fatty acids with = 0 to 2o carbon atoms in the molecule, which was created by the oxidation of paraffin, is heated to 200 ° with 22o g of zinc oxide. After diluting with q. kg engine oil is centrifuged in the heat. The product contains about 3.5 0 (a ash.

5. 1 kg of initial fatty acid from paraffin oxidation with an average 7 carbon atoms in the molecule is mixed with 6 kg of motor oil and while stirring Treated at 180 to 20 ° with 300 g of zinc hydroxide. The unresolved portions will be removed by centrifugation.

6. 1 kg of oleic acid is heated to 20 ° together with 2 kg of motor oil, 10 g of zinc hydroxide and 550 g of barium hydroxide until no more foaming occurs.

7. 1 kg of sperm oil fatty acid is mixed with 80 g of sulfur for half an hour heated to = 50 ° and then mixed with 180 g of zinc hydroxide. After heating up = 80 °, 2 kg of engine oil are added. It is centrifuged to remove undissolved parts. An oily product is obtained with about q. 0 / ö ashes.

8 .. - 1 kg of stearic acid is added for one hour with 80: g of sulfur Heated to 180 ° and then stirred with zoo g of zinc hydroxide at = q.ö to = 80 °. After this Mixing q kg of engine oil is centrifuged in the heat.

As a second component that is added to the lubricating oils according to the invention, come the. Oil-soluble reaction products of phosphorus pentasulfide with organic ones Hydroxyl compounds in question, e.g. B. with amyl alcohol, hexanol, octanol, dodecanol, Stearyl alcohol, montanol, oleyl alcohol, cyclohexanol, methylcyclohexanol, cyclohexylcyclohexanol, Benzyl alcohol, phenylethyl alcohol or abietinol. Also mixtures of higher alcohols, as in the isobutyl alcohol synthesis from carbon oxide and hydrogen or by Reduction of coconut oil or paraffin fatty acids are obtained suitable starting materials for the production of the phosphorus pentase conversion products. Likewise, alkylphenols, e.g. B. isobutyl, isoamyl, heptyl, octyl, dodecyl phenol or paraffin alkylphenols, which are formed by the condensation of chlorinated paraffin with phenol, Cresol or naphthol were produced in the presence of aluminum chloride as starting materials to serve. Even those from these alkylphenols by reaction with sulfur chlorides obtained alkylphenol sulfides or -disulftde as well as those made from them, still free hydroxyl containing esters, e.g. B. monoacetic acid, monopropionic acid or Monostearic acid esters of isobutylphenol sulfide can be used for the production of phosphorus pentasulfide reaction products be used.

The implementation of these compounds or their mixtures with phosphorus pentasulfide occurs at temperatures around 100 ° or slightly higher; e.g. at = 2o to r40 °. Instead of of these reaction products with phosphorus pentasulfide, their salts can also be used. As salt-forming bases come into question: ammonia, methylamine, diethylamine, Butylamine, stearylaxnine, ethylenediamine, hexamethylenediamine, diethylenetriamine, polymeric Ethylenimine, cyclohexylamine, benzylamine, phenylethylamine, aniline, quinoline, piperidine or alkaline earth metals, magnesium, zinc, aluminum, lead, tin or mixtures of these Fabrics.

Examples of suitable phosphorus pentasulfide reaction products are: I. Polyethyleneimine salt of a reaction product of phosphorus pentasulphide with paraffin alkylphenol, obtained from chlorinated paraffin and phenol and treated with S, C4.

IL The barium compound of the acetylated compound reacted with phosphorus pentasulfide Isobutyl phenol sulfide. III. The zinc compound of the reacted with phosphorus pentasulfide Stearic acid ester of isobutyl phenol sulfide.

IV. A product prepared as follows: 1 kg of stearyl alcohol is heated to 160 °, stirred with 300 g of phosphorus pentasulfide and heated further to 180 °. After the solid fractions have been removed by decanting, the mixture is cooled to ig.10 ° and admixed with 250 g of barium hydroxide containing water of crystallization with stirring. As soon as the foaming has stopped, it is filtered. After cooling, the product is a solid white mass. Instead of the barium hydroxide, 50 g of a 50% aqueous polyethyleneimine solution can be used.

V. A product prepared as follows: ¢ kg of from 220 to 2q.0 ° boiling alcohols obtained in the isobutyl alcohol synthesis are mixed with 1 kg of phosphorus pentasulphide with stirring for about 1/2. Heated to 125 to igo ° for an hour. 500 g of fuller's earth and 500 g of crystallized barium hydroxide are then added over the course of 2 hours at 120 ". After the reaction has ended, it is filtered.

VI. A product which has been obtained by treating 1 kg of isooctylphenol with 270 g of phosphorus pentasulphide at 120 to 150 ° and mixing with 2 kg of motor oil and 120 g of zinc hydroxide with heating until foaming and centrifugation cease.

Both the carboxylic acid zinc salts and the phosphorus pentasulfide reaction products are expediently used in a clear solution. Insoluble parts, even if they are cause only a turbidity of the solution, are advantageously filtered or centrifuged, if necessary after dilution with other solvents, removed. If you use if benzene or toluene are used, these are expedient after the solid components have been separated off to be distilled off in vacuo.

The two lubricating oil improvers are advantageously used in one Lubricating oil which is of a similar nature to that to be improved, dissolved and in this easy-to-use form applied. The amount of solvent used Lubricating oil depends on the solubility of the substances used. That’s enough z. B. for zinc oleate and zinc salts of similar unsaturated acids about the same Amount of lubricating oil, while zinc salts of saturated acids, e.g. B. zinc stearate, something need larger amounts of oil to dissolve.

How much of each individual lubricating oil improver to add depends on the type of lubricating oil and the requirements that are placed on this can be made. The cheapest amount can easily be found through preliminary tests determine. For high-performance lubricating oils z. B. more concentrated solutions are used than for the usual machine lubricating oils. As a rule, one of the carboxylic acid zinc salts is used Quantities between 0.05 and 5 "/ o, but in special cases also OK can be up to 15%, while of the phosphorus pentasulfide reaction products o, oi to 2%, based on the lubricating oil to be improved, can be added. Except The substances mentioned can be combined with other lubricating oil-improving oils at the same time Add substances, e.g. B. Salts of metals of the 2nd to q .. group of the periodic System with fatty acids containing i to q: carbon atoms in the molecule, e.g. B. Zinc propionate or tin butyrate. You can also use small amounts of anti-foaming agents Substances, e.g. B. silicone oil, add.

The lubricating oil improvers mentioned effect, if they are in accordance with of the invention are used together that deposits on the metal surfaces of the engine and that the piston rings do not get stuck. These Benefits are also obtained in diesel engines, even if they are high in sulfur Fuels are operated. The bearings are also used when working according to the invention Much more spared than when working without the substances mentioned or with only one of them. Harmful corrosion does not occur, rather the bearings show evenly retracted running surfaces.

Such good effects are z. B. achieved when the above-mentioned zinc salts and phosphorus pentasulphide reaction products are added in the following combinations to an engine oil to be used in a diesel engine: i to 3% zinc salt and 0.7% reaction product V, 2 to q. % Zinc salt 2 and 0.5% reaction product IV, 3 to 8% zinc salt 3 and 1% reaction product III, 3 to 8% zinc salt 3 and 0.7 to 0.9% a reaction product V, 1 , 5 to 5 per cent. Zinc salt q. and 1.5% reaction product VI, 2.5 to 6% of zinc salt 5 and 1 to 2% of reaction product I, 2 to 4% of zinc salt 6 and 1 to 2% of reaction product 1I, 2 to q . % Zinc salt 7 and 0.5 to 10%, reaction product V, 2 to 7% zinc salt 8 and 0.5 to i% of reaction product V, 2% zinc salt-i, 2% of a 5% solution of zinc propionate in lubricating oil and 0.7 0,! o conversion product V.

Claims (3)

PATENT CLAIMS: i. Lubricating oils, characterized by a content of oil-soluble zinc salts of carboxylic acids with at least 5 carbon atoms in the Molecule and oil-soluble reaction products of phosphorus pentasulphide with organic Hydroxyl compounds. 2. Lubricating oils according to claim i, characterized in that the phosphorus pntasulfide reaction products are used in the form of their salts. 3. Lubricating oils according to claim i and 2, characterized in that it is still anti-foaming Contains funds.