DE1076299B - Lubricating oils - Google Patents

Description

Lubricating oils It is known that lubricating oils can be added by adding so-called Detergents can improve. The detergents hold up when you use the oils occurring decomposition and condensation products in an even distribution, whereby Deposits on the metal surfaces of the engine can be avoided. These detergents generally consist of metal-containing organic compounds.

It has been found that lubricating oils with a high detergent effect can be used Addition of a mixture of a) reaction products of compounds with between one Ring system and an unsaturated side chain lying conjugated unsaturated Bonds with sulfur and smaller amounts, based on the unsaturated compounds and sulfur, on alkylphenols or their sulfides with b) as lubricating oil additives known reaction products of hydrocarbons or oxygen, nitrogen, sulfur- and / or halogen-containing organic compounds with phosphorus sulfides receives. As compounds with between a ring system and an unsaturated side chain lying conjugated unsaturated bonds come into consideration styrene, alkylstyrenes, Oxystyrenes, vinyl carbazole or other aromatic vinyl compounds and stilbene.

According to the invention, in addition to sulfur, alkylphenols are used in the condensation or their sulfides are added in small amounts. Appropriately one uses this z. B. 5 to 30 percent by weight, advantageously 10 to 20 percent by weight, based on the unsaturated compounds and sulfur. When using larger amounts of alkylphenols or their sulfides, less effective additives are obtained.

When carrying out the condensation, care must be taken that no strong polymerization of the unsaturated compounds takes place. Products, which polymerize too quickly for themselves and too high K values (F i k e n t s ch e r , Cellulosechemie, 1932, Vol. 13, p. 58) can be achieved by adding small amounts Amounts of stabilizers are prevented from polymerizing too quickly. It is therefore it is expedient to introduce the compounds mentioned into the molten sulfur. In addition to sulfur, you can also use sulfur-releasing compounds, such as. B. sulfur halides, Thionyl chloride, sulfuryl chloride, or phosphorus sulfide, or those that donate sulfur Use fabrics on their own.

The condensation is generally advantageous at 150 to 250 ° C below 200 ° C, e.g. B. at 160 to 180 ° C carried out. If there are other condensation agents are to be used, there are mainly weakly condensing substances, such as zinc oxide, zinc chloride, boron fluoride; Hydrogen halide, substances with a large surface area and small amounts of the more powerful condensing agents such as aluminum chloride and its complex compounds.

The reaction products obtained are ash-free compounds with a high sulfur content of about 10 to 25 percent by weight; they make oils from the viscosity of a lubricating oil: To the lubricating oils which the invention If they contain additives to make them resistant to oxidation, they are also given in small quantities of reaction products known as lubricating oil additives, so-called inhibitors, from hydrocarbons or organic ones containing oxygen, nitrogen and / or halogen Compounds with phosphorus sulfides to '.

Come as organic compounds for: the manufacture of inhibitors Alcohols as described in German Patent 843 281; as cyclic hydroxyl compounds into consideration. Furthermore, there are also single and straight rbasics Saturated or unsaturated aliphatic acids, hydroxy acids, expediently alkylated aromatic or ardliphatic acids, which can contain sulfur or halogen, Amino acids, keto or aldehyde acids, sulfonic acids, thio acids, acid amides, thiophenols, Dioxybenzenes and polyoxybenzenes are suitable. You can also get saturated and unsaturated Use ethers, thioethers, aldehydes, ketones. The acids mentioned can also be used with be esterified mono- or polybasic alcohols. Also esterified alkylphenol sulfides as well as xanthates and their reaction products with chlorides of sulfur or ethylene chloride are suitable. As halogen- or nitrogen-containing organic compounds come into consideration z. B. halogenated hydrocarbons or their derivatives, also amines, polyamines, hydroxylamines, thionylamines, alkylated ureas, thioureas, Thiocarbamic acid, aminophenols, amino alcohols. There are also oil-soluble higher-boiling ones Hydrocarbons such as paraffins, heavy oils, fatty oils, polymerisation products of paraffinic or aromatic olefins, condensation products of olefins and / or halogenated hydrocarbons, optionally with cyclic hydrocarbons, or condensation products of aldehydes and phenols, which are useful with paraffins are alkylated, as well as terpenes. These are at 50 to 200 ° C, in particular 70 to 150 ° C, with 3 to 50 percent by weight, in particular 5 to 20 percent by weight, a phosphorus sulfide, e.g. B. phosphorus pentasulfide heated.

The inhibitors obtained can be converted into their ammonium or amine salts, z. B. with organic nitrogen bases, transfer.

As such are e.g. B. piperazine, piperidine, isobutylamine, hexylamine, Octylamine, decylamine, dodecylamine, octodecylamine, methylcyclohexylamine, abietinylamine, Octodecylmethylamine and Octodecyldimethyl-benzyl-ammonium hydroxide and choline or phosphatides such as lecithin are suitable. But you can also use the alkaline earth, zinc, Tin, aluminum, cobalt, chromium and nickel salts of the reaction products for neutralization use.

For the preparation of these compounds used according to the invention no protection is claimed in the context of the present invention.

Small amounts of known anti-foaming agents can also be added to these products Add substances such as silicone oils.

According to the German patent specification 927 820, oil-soluble reaction products are of liquid, acyclic olefins with sulfur together with organic nitro compounds Lubricating oils added to increase high pressure lubricity.

From the German patent specification 926 680 is known sulphurized low molecular weight olefins, which are substituted by aromatic radicals, together to use with organic nitro compounds as lubricating oil additives, whereby the Push-up lubricity is improved. As such olefins are styrene and Called stilbene.

According to U.S. Patent 2,574,994 and British Patent 669 206 are said to have sulfurized long chain olefins used to improve lubricating oils be used.

In contrast, according to the present invention, the sulfurized Olefins not together with nitro compounds, but together with reaction products of organic carbonaceous compounds with phosphorus sulfides are used. This Lubricating oil additive mixture, which consists of a mixture of an ash-free (component a) and an ash-containing (component b) compound and thus in total can be described as low-ash, has a particularly good detergent effect.

The parts mentioned in the following example are parts by weight.

Example 150 parts of sulfur are used together with 150 parts of octylphenol and 60 parts of zinc oxide in a stirred tank at 170 ° C. To this mixture 600 parts of styrene are added within an hour. After adding 30 parts of zinc chloride the mixture is stirred for a further 1 hour, the temperature being lowered to 160.degree. Afterward the product is filtered or centrifuged. 855 parts of an ashless product are obtained Product that has a viscosity of 5.5 ° E / 50 ° C and a sulfur content of 16%. _ _ 18 parts of this product are mixed with 14 parts of a neutralized reaction product - A C, 3 alcohol from the -oxo synthesis with phosphorus pentasulfide and 68 parts of an engine lubricating oil mixed.

4.5 percent by weight of this mixture is used as a lubricating oil for diesel engines added. -The expansion findings after a long-term test in a four-stroke diesel engine, , which was carried out with such an alloyed engine oil, resulted in completely bare Pistons and no deposits of oil residues in the piston ring and oil scraper ring grooves.

The further test in the test strip apparatus (mineral oil technology, 1958, 36 ff.) Gave ratings of 9.5.

Claims (1)

PATENT CLAIM: Lubricating oils characterized by a content of Mixture of a) reaction products of compounds with between a ring system and conjugate unsaturated bonds lying on an unsaturated side chain with sulfur and smaller amounts, based on the unsaturated compounds and Sulfur, alkylphenols or their sulfides; with b) as lubricating oil additives known reaction products of hydrocarbons or oxygen, nitrogen, sulfur- and / or halogen-containing organic compounds with phosphorus sulfides as well as their alkaline earth, zinc, tin, aluminum, cobalt, chromium or nickel salts. Considered publications: German Patent Specifications Nos. 947 419, 934185, 933 048, 929 384, 927 820, 927 819, 926 680; U.S. Patent No. 2,574,994; British U.S. Patent No. 669,206.