DE1034799B - Lubricating oils - Google Patents

Description

Lubricating oils It is known, reaction products of hydrocarbons with phosphorus sulfides, expediently after conversion into metal salts, as lubricating oil additives to use.

It is also known, stabilized reaction products of unsaturated Hydrocarbons, e.g. B. to add styrene with phosphorus sulfides to mineral oils. aside from that has already been proposed, copolymers of styrene and isobutylene with phosphorus pentasulfide to be used as lubricating oil additives. Finally, products were also made by Reaction of olefins with phosphorus sulfides in the presence of water were obtained, described as additives for lubricating oils.

It has now been found that reaction products of mineral oil soluble Polystyrene with phosphorus sulfides, e.g. B. phosphorus pentasulphide and phosphorus sesquisulphide, Lubricating oil improvers are of particular effectiveness. Mineral soluble polystyrenes can be obtained, for example, by polymerization with boron fluoride. they are highly viscous products with a balsam-like consistency and lower average molecular weights than the solid styrene polymers; the mineral oil-soluble polystyrenes to be used can for example have an average molecular weight of 3000, 5000 or 8000. It is essential that the starting materials in mineral oils such. B. engine lubricating oils, are soluble.

The reaction products can be prepared by heating mineral oil-soluble Polystyrene made with phosphorus sulfides, temperatures are suitable at where hydrogen sulfide is split off (e.g. 150 to 200 ° C). There The mineral oil-soluble polymeric styrenes are usually very highly viscous, it is generally preferable to carry out the reaction in the presence of suitable solvents.

A solvent that can be used under the conditions necessary for the reaction practically does not react with the phosphorus sulfides is decahydronaphthalene; the one Presence in the lubricating oil can interfere due to the low flash point, it is advisable to to distill off the decahydronaphthalene from the reaction mixture. Becomes beneficial the decahydronaphthalene distilled off after adding lubricating oil, a solution of the reaction product is obtained in the lubricating oil.

But you can also use those solvents with the phosphorus sulfides react, e.g. B. tetrahydronaphthalene, olefins, terpenes, alcohols, alkylphenols, Alkylphenol sulfides, ketones, esters.

The easiest way to work is when using lubricating oils as a solvent; in this case, the reaction product is directly in the form of a get a concentrated lubricating oil solution that dissolves easily in additional lubricating oil, and it is not necessary to distill off solvents. The one for implementation Required amounts of phosphorus sulfide can be different, e.g. B. 5 to 30 percent by weight of polystyrene. It is advisable not to use large amounts of phosphorus sulfide, to prevent the formation of dark, resinous by-products.

After the reaction has ended, those in the reaction are separated into small amounts Amounts formed insoluble; Divide from the reaction mixture by this Allow parts to settle or throw them off. The separation is made by mild heat and addition of solvents accelerated.

It is very advantageous to treat the reaction products with large surface areas Substances, e.g. B. Terrana, activated carbon or silica gel in the heat, in particular at about 50 to 250 ° C, advantageously 100 to 150 ° C. This treatment can be done after the Separation of the insoluble fractions formed during the reaction can be carried out but also let the large-surface substances act on the reaction mixture and the insoluble resinous ones formed upon exposure to phosphorus sulfide Separate the fabrics together with the large-surface fabrics. The amount of applied Large surface materials can fluctuate within wide limits, for example they can 1 to 50%, advantageously 3 to 20 l) / ,.

The described reaction products of mineral oil-soluble polystyrene with phosphorus sulfide, engine lubricating oils give the property of impurities, which form or get into the oil during engine operation, in suspension and to keep the engine bright; the conversion products can be shared with others Lubricating oil additives, e.g. B. Phosphorus sulfide reaction products with other hydrocarbons, Alcohols, alkylphenols, alkylphenol sulfides or amines, as well as VI improvers, Pour point depressants and anti-foaming agents can be used. For the production of those used according to the invention as a constituent of lubricants No protection is claimed for compounds in the context of the present invention.

Example 1 A mineral motor oil in the viscosity range SAE 20 is used to lubricate a gasoline engine that runs on leaded gasoline will; To test the oil under severe conditions, the oil temperature is set to 130 ° C held. Before the start of the actual test run, the engine is allowed to run in for 8 hours. If the piston is removed after 36 hours of operation, the exterior of the piston is preserved grade 2 on the Lauson scale.

You lubricate the engine with the same oil, the 2.2 percent by weight of the additive, the preparation of which is described below, so the piston receives a grade of 1.1 after a test run under the same conditions.

The additive is obtained in the following way: 50 parts by weight Mineral oil-soluble polystyrene obtained by polymerizing styrene using obtained from boron fluoride as a catalyst and having a k value of 18 or less has, are dissolved in 150 parts by weight of decahydronaphthalene; the solution will be several Hours heated to boiling with 10 parts by weight of phosphorus pentasulfide under reflux, until no more hydrogen sulfide is evolved. Then 300 parts by weight Benzene added. After 24 hours it will be deposited from the brown, resinous Portions decanted off, mixed with 450 parts by weight of engine lubricating oil and cooked through Distilling under normal, then under reduced pressure of benzene and decahydronaphthalene freed. After adding 5 parts by weight of Terrana while stirring briefly at 100 to 120 ° C is filtered hot, whereby a clear, light brown product is formed, which is about Contains 10% active ingredient.

A similar product with the same effectiveness is created if one right at the beginning the polystyrene dissolves in lubricating oil instead of decahydronaphthalene and otherwise proceed accordingly.

EXAMPLE 2 A diesel engine is lubricated with a mineral motor oil, 2% of the product described in Example 1, penultimate paragraph, and 0.4% of a zinc compound of a reaction product of coconut alcohol and phosphorus pentasulphide which is aftertreated with Ca 0 and H 0 Applied approximate Salary of Vers. Type of amount of additive Evaluation No. Additive additive to active ingredient note Corresponds to (Weight- (weight- percent) percent) - 1 A 0.02 50 6.5 British Patent 693 422, Example 2 2 A 0.03 50 7.5 the same. 3 A 0.05 50 6.5 the same. 4 B 0.03-100 6.0 U.S. Patent 2,534,217, Example 4 5 B 0.05 100 8.0 the same. 6 B 0.1 100 5.5 the same. 7 C 0; 5 100 7.0 U.S. Patent 2,494,592, Example 2 8 C 1 100 8.5 like. 9 C 1.5 100 6.0 same 10 D 1.5 10 7.0 Present patent application, example 1 11 D 2 10 9.5 the same. 12 D - - 2; 5 10 9,0 the same. was added. The piston of the engine is much lighter after 100 hours of operation than when using the base oil alone; the sticking of piston rings and the formation of heavy deposits in the ring grooves and the slots of the oil control rings, which occurs when using the base oil alone, is avoided when using the oil with the additives mentioned.

British Patent 693 422 discloses additives for mineral oils known that by stabilizing reaction products of unsaturated hydrocarbons obtained with phosphorus sulfides; the stabilization is done either by Exposure to normal alcohols with at least 4 carbon atoms in the molecule or by treatment with basic substances or by halogen treatment. For one A comparison with the lubricating oil additives claimed according to the invention was made Substance used, according to the information in Example 2 of the British Patent specification by reacting turpentine with phosphorus pentasulphide, action obtained from butanol, diluting with mineral oil and filtering with the addition of silica gel had been. This additive is designated A in the table below.

US Pat. No. 2,534,217 describes lubricating oil additives, by reacting 1 mole of olefin with 0.2 to 2.0 moles of a phosphorus sulfide in the presence of water (0.5 to 3 moles per mole of phosphorus sulfide). For the comparative experiments, a product was used, which according to Example 4 of mentioned USA.-Patent and in the following table is denoted by B.

According to US Pat. No. 2,494,592, inter alia, copolymers are used made of styrene and isobutylene with phosphorus pentasulphide converted to lubricating oil additives. A manufactured according to Example 2 of the USA patent, hereinafter referred to as C Product was used for comparison with a lubricating oil additive claimed according to the invention used.

That in example 1 of the present patent application was used as a comparative product Phosphorus pentasulfide reaction product of oil-soluble polystyrene described in hereinafter referred to as D.

The four products mentioned were tested in a lubricating oil testing device according to German patent specification 888 622. The base oil was a German Mineral motor oil of the viscosity range produced by selective refining SAE 20 used. Of each of the additives mentioned were made solutions different concentrations in the oil mentioned and determined which Oils gave the best ratings in the testing apparatus mentioned. The test results are compiled in the table above. The best possible rating in this test is 10, the worst 1. The base oil alone gives the grade 5.0. Since some of the additives compared contain mineral oil as a diluent, the table, column 4, indicates the active substance content of the additives have about.

From the table it can be seen that with what is claimed according to the invention The product receives the best rating.

Claims (2)

PATENT CLAIMS: 1. Lubricating oils, characterized by a content of reaction products of mineral oil-soluble polystyrene with phosphorus sulfides. 2. Lubricating oils according to claim 1, characterized in that the reaction products have been subjected to treatment with substances with a large surface area. References considered: U.S. Patent Nos. 2,494,592, 2,534,217; British Patent No. 693 422.