NL8003282A - Molybdenum compounds, processes for their preparation and lubricating oil compositions containing these compounds. - Google Patents

Description

J

H.O. 29.099

Molybdenum compounds, processes for their preparation as well as lubricating oil preparations. containing these compounds, _

The present invention relates to new lubricating oil preparations. More particularly, the invention relates to novel lubricating oil compositions, which include antioxidant molybdenum? contain compounds.

Molybdenum disulfide has long been known as a desirable additive to lubricating oil formulations. However, one of the main drawbacks is its lack of oil solubility. Molybdenum disulfide is usually finely milled and then dispersed in the lubricating oil formulation to impart friction modifying and anti-wear properties. Finely ground molybdenum disulfide is not an effective oxidation inhibitor in lubricating oils.

As an alternative to the fine grinding of the molybdenum disulfide, a number of different approaches involving the preparation of salts of molybdenum compounds have been attempted. One type of compound prepared is molybdenum dithiocarbamates. Representative formulations are described in U.S. Patent 3,412,589) which discloses molybdenum (Y1) dioxide dialkyldithiocarbons, U.S. Patent 3 * 509 * 051) which describes sulfurized oxymolybdenum dithioearbamates, and U.S. Patent 4 * 098,705) which contains sulfur containing molybdenum dihydrocarbon dithiocarbamate preparations have been described.

Another approach is the formation of dithiophosphates instead of dithiocarbamates. Representative of this type of molybdenum compound are the compositions disclosed in U.S. Pat. No. 3,494,866, such as oxymolybdenum diisopropylphosphorodithioate.

U.S. Pat. No. 3,184,410 discloses certain dithiomolybdenylacetylacetonates for use in lubricating oils.

Braithwaite and Greene in Wear, 46 (1978), 405-452 describe various molybdenum-containing compositions for use in engine oils.

U.S. Pat. No. 3,554,910 discloses a molybdenum trioxide complex with diethylene triamine for use as an additive to molten steel.

Russian Patent 555 * 625 describes lubricating oil additives prepared from ammonium molybdate and alkenylated polyamines.

Another way of incorporating molybdenum compounds in oil is to prepare a colloidal complex of molybdenum disulfide or oxysulfides dispersed using known dispersants. U.S. Pat. No. 3,223,625 discloses a process in which an acidic aqueous solution of certain molybdenum compounds is prepared and then extracted with a hydrocarbon ether dispersed with an oil-soluble dispersant and then freed from the ether.

US patent 3 * 281,355 describes the preparation of a contact of a dispersion of molybdenum disulfide by preparing a mixture of lubricating oil, dispersant and a molybdenum compound in water or in an aliphatic alcohol containing 1 to 4 carbon atoms sulfide ion-developing compound and then solvent removal, dispersants which are effective in this process include petroleum sulfonates, phenates, alkylphenate sulfides, phosphosulfurized olefins, and combinations thereof.

It has been found that a lubricating oil additive can be prepared by combining an acidic molybdenum compound, a basic nitrogen-containing preparation, preferably in the presence of a polar promoter and a sulfur source to form a molybdenum and sulfur-containing complex.

Lubricating oil compositions containing the additive prepared as described herein are useful as liquid and lubricating compositions (depending on the specific additive or additives used) for inhibiting oxidation, imparting anti-wear and EP properties and / or modifying the frictional properties of the oil which, when used as a crankcase lubricant, lead to improved mileage.

The exact molecular formula of the molybdenum preparations of the present invention is not known with certainty; however, they are believed to be compounds in which molybdenum, the valences of which are occupied with oxygen or sulfur atoms, has been complexed by either the salt of one or more nitrogen atoms of the basic nitrogen-containing preparation used for the preparation of these preparations.

The molybdenum compounds used for the preparation of the compositions of the present invention are acidic 40 molybdenum compounds.

800 3 2 82 5 "

Acid is understood to mean that the molybdenum compounds will react with a basic nitrogen compound as measured by the titration method of ASTM Test D-664 or D-2896. Usually, these molybdenum compounds are hexavalent and are represented by the following compositions: molybdenumic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts such as hydrogen salts, for example sodium hydrogen molybdate, MoOCl2, MoO2 Br2? III, Clg, molybdenum-10 trioxide or similar acidic molybdenum compounds. Preferred acidic molybdenum compounds are molybdenumic acid, ammonium molybdate and the alkali metal molybdates.

Especially preferred are molybdenoic acid and ammonium molybdate.

The basic nitrogen compound should have a basic nitrogen content, as measured according to ASTM D-664 or B-2896. The compound is preferably oil-soluble. Usual formulations are suecinimides, carboxylic acid amides, hydrocarbon monoamines, hydrocarbon polyamines, Mannich bases, phosphonamides, thiophosphonamides, phosphoramides, the viscosity index of a dispersant improvers and mixtures thereof. These basic nitrogen-containing compounds are described below (with the caveat in mind that each must contain at least one basic nitrogen atom). Any of the nitrogen-containing compositions can be post-treated with, for example, boron, by methods known in the art, as long as the compositions continue to contain basic nitrogen. These aftertreatments are particularly applicable to succinimides and Mannich base preparations.

The mono- and polysuccinimides which can be used for the preparation of the lubricating oil additives as described herein have been described in numerous places and are known in the art. Certain basic types of succinimides and related products, which are encompassed by the term "succinimide" are described in U.S. Pat. Nos. 3 * 219,666, 3,172,892, and 3,272,74-6. The term "succinimide" is understood to include many of the amide, imide, and amidine species also formed by this reaction 40. However, the predominant product is a succinimide and this expression is generally accepted as "meaning of the reaction product of an alkenyl-substituted succinic acid or anhydride with a nitrogen-containing compound. Preferred succinimides for their commercial availability are those succinimides prepared from a hydrocarbon succinic anhydride, wherein the hydrocarbon group contains about 24 to about 350 carbon atoms, and an ethyleneamine, which ethylene amines are particularly characterized by ethylene -10 diamine, diethylene triamine, triethylene tetramine and tetraethylene pentamine. Especially preferred are those succinimides prepared from polyisobutenyl succinic anhydride of 70 to 128 carbon atoms and tetraethylene pentamine or triethylene tetramine or mixtures thereof.

Also included by the term succinimide are the co-oligomers of a hydrocarbon succinic acid or anhydride and a poly-secondary amine containing at least one tertiary amino nitrogen in addition to two or more secondary amino groups. Usually this preparation has an average molecular weight of between 1500 and 50,000. A conventional compound will have been prepared by reacting polyisobutenyl succinic anhydride and ethylene dipiperazine. Compositions of this type are described in U.S. Patent Application No. 816,063, July 15, 1977.

Carboxylic amide preparations are also suitable starting products for the preparation of the products of the present invention. Compounds of this type are described in U.S. Pat. No. 3,405,064. These preparations are usually prepared by reacting a carboxylic acid or anhydride or ester with at least 12 to about 350 aliphatic carbon atoms in the aliphatic main chain and optionally with sufficient pendant aliphatic groups to make the molecule soluble in oil, with an amine or a hydrocarbon polyamine, such as an ethylene-35 amine, to give a mono- or polycarboxylic acid amide. Preferred are the amides prepared from (1) a carboxylic acid of the formula S ^ COOH, which represents an alkyl group of 12 to 20 carbon atoms or a mixture of this acid with a polyisobutenyl carboxylic acid, wherein the polyisobutenyl group contains from 40 to 128 carbon atoms and (2 ) an ethylene amine, especially triethylene tetramine or tetraethylene pentamine, or mixtures thereof.

Another group of compounds useful in the present invention are hydrocarbon polyamines, preferably of the type described in U.S. Pat. No. 3,574,576. The hydrocarbon radical, which is preferably alkyl or olefinic with one or two unsaturation sites, usually contains from 9 to 350, preferably from 20 to 200, carbon atoms. Particularly preferred hydrocarbon polyamines are the polyamines derived, for example, from the conversion of polyisobutyl chloride and a polyalkylene polyamine, such as an ethylene amine, eg ethylene diamine, diethylene triamine, tetraethylene pentamine, 2-aminoethylpiperazine, 1.3-propy -15 lentiamine, 1,2-propylenediamine and the like.

Another group of compounds suitable for providing basic nitrogen are the Mannich base preparations. These preparations are prepared from a phenol or an alkyl phenol of 9 to 200 carbon atoms, an aldehyde such as formaldehyde or formaldehyde precursor such as paraformaldehyde, and an amine compound. The amine can be a mono- or polyamine and conventional preparations are prepared from an alkylamine, such as methylamine or an ethylene amine, such as diethylene triamine or tetraethylene pentamine and the like. The phenolic product can be sulfurized and is preferably dodecyl phenol or an alkyl phenol with 80 to 100 carbon atoms. Conventional Mannich bases that can be used in the present invention are described in U.S. Patent Application No. 838,197, September 30, 1977, and U.S. Pat. Nos. 3,649,229, 3,368,972, and 5,539,663. The last application describes Mannich bases prepared by reacting an alkyl phenol of at least 50 carbon atoms, preferably 50 to 200 carbon atoms, with formaldehyde and an alkylene polyamine HN (ANH) nH, wherein A 35 represents a saturated divalent alkyl hydrocarbon group of 2 to 6 carbon atoms and n is 1 to 10 and wherein the condensation product of the alkylene polyamine can be further reacted with urea or thiourea. The use of this Mannich base as starting materials for the preparation of 40 lubricating oil additives can often be significantly improved

O ft Λ 7 O OO

u by treating the Mannich base using conventional techniques to incorporate boron into the composition.

Another formulation group suitable for preparing the additives of the present invention are the phosphoramides and phosphonamides as described in U.S. Pat. Nos. 3,909.4-30 and 3,968,157. These preparations can be prepared by forming a phosphorus compound with at least P-N bond. For example, they can be prepared by reacting phosphorus oxychloride with a hydrocarbon diol in the presence of a monoamine or by reacting phosphorus oxychloride with a difunctional secondary amine and a monofunctional amine. Thiophosphoramides can be prepared by reacting an unsaturated hydrocarbon compound containing from 2 to 450 or more carbon atoms, such as polyethylene, polyisobutylene, polypropylene, ethylene, 1-hexene, 1,3-hexadiene, isobutylene, 4- methyl pentene-1 and the like, with phosphorus pentasulfide and a nitrogen-containing compound as defined above, especially an alkyl amine, alkyl diamine, alkyl polyamine or an alkylene amine such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and the like.

Another group of nitrogen-containing preparations suitable for the preparation of the molybdenum preparations of the present invention includes the so-called viscose. enhancement index improvers with dispersive compression (YI improvers). These VI improvers are usually prepared by functionalizing a hydrocarbon polymer, especially a polymer derived from ethylene and / or propylene, optionally containing additional units from one or more comonomers, such as alicyclic or aliphatic olefins or dialkenes. The functionalization can be carried out by various methods, which introduce a reactive site or reactive sites, which usually have at least one oxygen atom on the polymer. The polymer is then contacted with a nitrogen-containing source to introduce nitrogen-containing functional groups to the polymer backbone. Nitrogen sources commonly used include basic nitrogen compounds, in particular the 800 3 2 82 7 'nitrogen-containing compounds and preparations described herein. Preferred nitrogen sources are alkylene amines such as ethylene amines, alkylamines and Mannicb bases.

Preferred basic nitrogen compounds for use in the present invention are succinimides, carboxylic acid amides and Mannich bases.

Representative sulfur sources are sulfur, hydrogen sulfide, sulfur monochloride, sulfur dichloride, phosphorus penta sulfide, where there is one primary hydrocarbon group, preferably alkyl having 1 to 40 carbon atoms, and x being at least 2, inorganic sulfides and polysulfides such as wherein x at least 1 is thioacetamide, thiourea and mercaptans of the formula RSH, wherein R is as defined above. Also suitable as sulfurizing agents are the conventional sulfur-containing antioxidants, such as wax sulfides and polysulfides, sulfurized olefins, sulfurized carboxylic acid esters and sulfurized ester olefins, and sulfurized alkyl phenols and their metal salts.

The sulfurized fatty acid esters are prepared by reacting sulfur, sulfur monochloride and / or sulfur dichloride with an unsaturated fatty acid ester under elevated temperatures. Conventional esters include alkyl esters of 1 to 20 carbon atoms in the alkyl group of unsaturated fatty acids of 8 to 24 carbon atoms, such as palmitoleic acid, oleic acid, ricinoleic acid, petroselic acid, vaccenic acid, linoleic acid, linolenic acid, oleostearic acid, licanoic acid, paranoic acid, tariric acid, gadolic acid, arachidonic acid, cetolic acid, etc. Particularly good results have been obtained with mixed unsaturated fatty acid esters, such as obtained from animal fats and vegetable oils, such as tall oil, linseed oil, olive oil, castor oil, groundnut oil, rapeseed oil, fish oil, spermaceti oil etc.

Examples of fatty acid esters include lauryl tallowate, methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate, lauryl rinoleate, oleyl linoleate, oleyl stearate and alkyl glycerides.

Cross-linked sulfurized ester olefins, such as a sulfurized mixture of olefins of 10 to 25 carbon atoms with fatty acid esters of fatty acids of 10 to 25 carbon atoms and al-40 alkyl or alkenyl alcohols of 1 to 25 carbon atoms, in which the on-7 o fatty acid and / or the alcohol is unsaturated , can also be used.

Sulfurized olefins were prepared by the reaction of an olefin having 3 to 6 carbon atoms or a low molecular weight polyolefin obtained therefrom with a sulfur-containing compound such as sulfur, sulfur monochloride and / or sulfur dichloride.

Also suitable are the aromatic and alkyl sulfides, such as dibenzyl sulfide, dixylyl sulfide, dicetyl sulfide, diparaffin wax sulfide and polysulfide, cracked wax olefin sulfides, etc. They can be prepared by treating the starting product, for example ethylenically unsaturated compounds, with sulfur, sulfur monochloride. Particularly preferred are the paraffin wax thiomers described in U.S. Pat. No. 2,334-6,156.

Sulfurized alkylphenols and their metal salts include preparations such as sulfurized dodecylphenol and its calcium salts. The alkyl group usually contains from 9 to 300 carbon atoms. The metal salt may preferably be a Group I or Group II salt of the periodic table, in particular sodium, calcium, magnesium and barium.

Preferred sulfur sources are sulfur, hydrogen sulfide, phosphorus pentasulfide, wherein R represents carbon-hydrogen, preferably alkyl of 1 to 10 carbon atoms, and x is at least 3, mercaptans, wherein R is an alkyl group of 1 to 10 carbon atoms inorganic sulfides and polysulfides, thioacetamide and thiourea.

Most preferred sulfur sources are sulfur, hydrogen sulfide, phosphorus pentasulfide and inorganic sulfides and polysulfides.

The polar promoter, which is preferably used in the method of the present invention, is a compound that facilitates the interaction between the acidic molybdenum compound and the basic nitrogen compound.

A wide variety of such promoters are known to the person skilled in the art. Common promoters are 1,3-propanediol, 1,4-butanediol, diethylene glycol, butyl cellosolve, propylene glycol, 1.4-butylene glycol, methylcarbiol 4-0 toluene, amineamine, diethanolamine, N-methyl diethanolamine, 800 32 82 9 dimethylformamide, ίΓ- methyl acetamide, dimethyl acetamide, methanol, ethylene glycol, dimethyl sulfoxide, hexamethylphosphoramide, tetrahydrofuran and water. Preference is given to water and ethylene glycol. Especially preferred is water.

While usually the polar promoter is separately added to the reaction mixture, it may also be present, especially in the case of water, as a component of non-anhydrous starting materials or as hydrate-10 in the acid molybdenum compound, such as (Μ ^) ^ Μ Water can also be added as ammonium hydroxide.

A method of preparing the compositions of the present invention is the preparation of a solution of the acidic molybdenum precursor and a basic nitrogen-containing compound, preferably in the presence of a polar promoter with or without diluent. The diluent is used, if necessary, to provide a suitable viscosity for easy stirring. Usual diluents are lubricating oil and liquid compounds containing only carbon and hydrogen. If desired, ammonium hydroxide can also be added to the reaction mixture to give a solution of ammonium molybdate. This reaction is carried out at a temperature from the melting point of the mixture to the temperature at which reflux takes place. The reaction is usually conducted at atmospheric pressure, although higher or lower pressures can be used if desired. This reaction mixture is treated with a sulfur source, as defined above, at an appropriate pressure and temperature for the sulfur source to react with the acidic molybdenum and basic nitrogen compounds. In some cases, removal of water from the reaction mixture may be desirable prior to the completion of the reaction with the sulfur source.

In the reaction mixture, the ratio of molybdenum compound to basic nitrogen compound is not critical; however, as the amount of molybdenum with respect to basic nitrogen increases, the filtration of the product becomes more difficult. Since the molybdenum component is likely to oligomerize, it is expedient to add as much molybdenum 800 32 82 as is easily maintained in the composition. Usually the reaction mixture will contain 0.01 to 2.00 molybdenum atoms per basic nitrogen atom.

Preferably 0.4 to 1.0 and most preferably 0.4 to 0.7 molybdenum atom per basic nitrogen atom is added to the reaction mixture.

The sulfur source is usually added to the reaction mixture in a ratio to provide 0.1 to 4.0 sulfur atoms per molybdenum atom. Preferably 0.5 to 3.0 sulfur atoms per molybdenum atom are added and most preferably 1.0 to 2.6 sulfur atoms per molybdenum atom.

The polar promoter, which is optionally and preferably used, is usually present in a ratio of 0.1 to 50 moles of promoter per mole of molybdenum. Preferably 0.5 to 25 and most preferably 1.0 to 15 moles of promoter per mole of molybdenum is present.

The lubricating oil compositions containing the additives of the present invention can be prepared by mixing the appropriate amount of molybdenum-containing preparation with a lubricating oil according to conventional techniques. The choice of the particular base oil depends on the intended use of the lubricant and the presence of other additives. Generally, the amount of molybdenum-containing additive will range from 0.05 to 15 wt%, and preferably from 0.2 to 10 wt%.

The lubricating oil that can be used in the present invention includes a wide variety of hydrocarbon oils, such as naphthene-based, paraffin-based, and mixed-base oils, as well as synthetic oils, such as esters and the like. Lubricating oils can be used individually or in combination and generally have a viscosity ranging from 50 to 5,000 SUS and usually from 100 to 15,000 SUS at 58 ° C.

In many instances, it may be effective to form concentrates of the molybdenum-containing additive within a carrier fluid. These concentrates provide an effective handling and transport method of the additives before their subsequent dilution and use. The concentration of the molybdenum containing additives in the concentrate may range from 0.25 to 90 wt%, although it is preferable to maintain a concentration between 1 and 50 wt%. The ultimate application of the lubricating oil compositions of the present invention may be in marine cylinder lubricants, such as in crosshead diesel engines, crankcase lubricants such as in automobiles and rail cars, heavy machinery lubricants such as steel processing equipment and the like or as bearing greases and the like. Whether the lubricant is liquid or solid will usually depend on whether a thickener is present. Common thickeners include polyurea acetates, lithium stearate and the like.

If desired, other additives may be included in the lubricating oil compositions of the present invention. These additives include anti-oxidants or oxidation inhibitors, dispersants, rust inhibitors, anti-corrosion agents, etc. Also anti-foaming agents, stabilizers, anti-coloring agents, adhesives, anti-vibration agents, drip-tip improvers, anti-grinding agents, EP-20 agents, odor control agents and the like are present.

Certain molybdenum products, which can be prepared by the process of the invention, can also be used in the manufacture of brake lining materials, high temperature structural materials, in iron and steel alloys, in coating materials, in electrolithic coating solutions, as components of electric discharge machine electrodes, as fuel additives, for the production of self-lubricating or wear-resistant structures as mold release agents, in preparations for phosphating steel, in soldering fluxes, in nutrient media for microorganisms, for the production of electro-sensitive recording material, in catalysts for refining coal, oil, clay shale, tar sands and the like or as stabilizers or hardeners for natural rubber or polymers.

Example I

To a 500 ml flask, 290 g of a solution of a 45% concentrate in oil of the succinimide were prepared from polyisobutenyl succinic anhydride and tetraethylene-40 pentamine and with a number average molecular weight for 800 32 82 of the polyisobutenyl group of about 980 and 150 ml of hydrocarbon. dust diluent added * The mixture was heated to 120 ° C * Then, over a period of 45 minutes at 100 to 110 ° C, a solution was added containing 28.8 g of molybdenum-5 trioxide dissolved in 12.9 g of concentrated ammonia. nium hydroxide diluted to 100 ml with water (0.21 mol ammonia). The reaction mixture was refluxed (about 155 ° C) and kept at this temperature for one hour. Hydrogen sulfide gas was fed at 115 ° C. In total 10 g of hydrogen sulfide were added and then the reaction mixture was purged with nitrogen at 110 ° C for one hour. The mixture was then heated to 1550C and held at this temperature for one hour. 100 ml of hydrocarbon diluent were added to the mixture and then the mixture was filtered hot through diatomaceous earth. The product was stripped to 160 ° C at 2.7 kPa to yield 516.6 g of product containing 4.94% molybdenum, 2.77% oxygen, 2.10% sulfur and 1.91% nitrogen.

Example II

A solution of 28.8 g of molybdenum trioxide dissolved in 0.2 mole of ammonia of 12.9 ml of concentrated ammonium hydroxide diluted to 100 ml with water was added dropwise at 100 to 105 ° C over a period of 45 minutes. 290 g of the succinimide described in Example I. The reaction mixture was refluxed at about 155 ° C and held at this temperature for one hour. The mixture was then heated to 140 ° C and 4 g of sulfur was added. The temperature was raised to reflux at 155 ° C under reflux for one hour. The temperature was then raised to 165-170 ° C and held for 2 hours. Then, 100 ml of hot hydrocarbon thinner were added to the mixture to give about 200 ml of solvent in the reaction flask. The mixture was filtered warm through diatomaceous earth and then stripped at 160 ° C and 2.7 kPa to yield 312.8 g of product containing 5% 39% molybdenum, 1.75% nitrogen, 3> 50% oxygen and contained 1.30% sulfur.

Example III

To a 1 liter flask, 290 g of the succinimide described in Example 40 and 150 ml of hydrocarbon thinner were added. The reaction mixture was heated to 65 ° C and 28.8 g of molybdenum trioxide and 50 ml of water were added. The temperature was kept at 65 to 70 ° C for 30 minutes and then raised to 150 ° C. After 50 minutes and 150 ° C, 5 g of elemental sulfur and 50 ml of hydrocarbon diluent were added. The temperature was raised to 155-160 ° C (reflux) over a 30 minute period. Some solvent was removed and the temperature was raised to 165-170 ° C. The mixture was kept at this temperature for 2 hours. 50 ml of hydrocarbon diluent were added to the mixture and the mixture was filtered through diatomaceous earth and then stripped piglet 160 ° C and 2.7 kPa to give 314.5 g of product, which is 4.93% molybdenum, 3 > 59%, 3> 4-8% oxygen, 1.92% nitrogen 15 and 1.4-9% sulfur.

Example IV

To a 1 liter flask, 290 g of the succinimide described in Example I and 150 ml of hydrocarbon thinner were added. The mixture was heated to 65 ° C and 28.8 g of molybdenum trioxide and 50 ml of water were added.

The temperature was held at 65 ° C for 30 minutes and raised to 150 ° C in 55 minutes. 7 g of elemental sulfur and 100 ml of hydrocarbon thinner were added to the mixture. The reaction mixture was refluxed at about 155 ° C for 4-5 minutes and then the temperature was raised to 165-170 ° C and held for 2 hours. 50 ml of hydrocarbon diluent were added to the mixture and the reaction mixture was filtered warm through diatomaceous earth.

The filtrate was stripped at 160 ° C and 2.7 kPa to yield 316.5 g of product containing 6.35% molybdenum,

Contains 3.57% oxygen, 1.86% nitrogen, and 2.15% sulfur. Example V

290 g of the succinimide, molybdenum trioxide, 50 ml of water and 150 ml of hydrocarbon thinner described in Example 1 were added to a 1 liter flask. The reaction mixture was heated to 65 ° C and held at this temperature for 30 minutes. Then 6 g of hydrogen sulfide at 63 DEG-65 DEG C. were added over 15 minutes. After the addition, the temperature was kept at 63-65 ° C for one hour with vigorous stirring and under a nitrogen atmosphere. The temperature was then raised to 100 ° C to remove most of the water and then refluxed to 155-160 ° C for one hour. The mixture was filtered warm through diatomaceous earth and then stripped to 160 ° C and 2.7 kPa to give 314.15 S of product containing 5 * 87% molybdenum, 3 * 64% oxygen, 2.05% nitrogen, Contains 0.75% sulfur and 0.08% sediment.

Example VI

To a 1 liter flask, 290 g of the succinimide described in Example I and 150 ml of hydrocarbon thinner were added. The mixture was heated to 65 ° C and 28.8 g of molybdenum trioxide and 50 ml of water were added.

The temperature was held at 65 ° C for 30 minutes and then slowly raised to 155 ° C. At 120 ° C, 10 g of elemental sulfur was added and the reaction mixture was held at 155 ° 0 for 30 minutes, at 160 ° C for 15 minutes, at 170 ° C for 30 minutes, at 175 ° C for 30 minutes and at 180 ° C for 30 minutes. . Then, 120 ml of hydrocarbon diluent were added and the reaction mixture was filtered through diatomaceous earth and the filtrate 20 was stripped at 160 ° C and 2.7 kPa to give a product containing 5 * 70% molybdenum, 2.88% oxygen, 1. Contains 83% nitrogen and 2.94% sulfur.

Example VII

To a 3 liter flask, 1160 g of the succinimide described in Example I and 800 ml of hydrocarbon thinner were added. The mixture was heated to 65 ° C and 200 ml of water and 116 g of MoO 2 were added. The temperature was raised to reflux (98 ° C) and held at this temperature for 2.5 hours until the solution turned pale green. Water was removed to a temperature of 140 ° C (bottom product). Then 60 g of sulfur were added. The temperature was raised to 155 ° C in 15 minutes and held at this temperature for 30 minutes. Then the temperature was raised to 180 ° C in 30 minutes and this temperature was maintained for 3 hours. The mixture was then cooled and left overnight. Then 200 ml of hydrocarbon thinner were added and the solution heated to 130 ° C. The solution was filtered through diatomaceous earth and stripped at 200 ° C and 2.7 kPa to give 1287 S product, containing 4.49% sulfur, 5 * 82% molybdenum, and 2.58% 800 3 2 82 15 contains oxygen.

Example VIII

To a 5 liter flask, 1160 g of a polyamide prepared from a carboxylic acid with 18 carbon atoms and 5 tetraethylene pentamine containing 6.29% nitrogen and 800 ml of hydrocarbon thinner were added. The mixture was heated to 65 ° C and 200 ml of water and 116 g of MoO 2 were added. The temperature was raised to reflux, about 95 ° C and held at this temperature for 4 hours until the solution turned pale green. The solvent was removed at a maximum of 150 ° C and the mixture was then cooled to 140 ° C and 28 g of sulfur were added. The temperature was raised to 155 ° C in 15 minutes and held at this temperature for 30 minutes. The temperature was raised again to 175 ° C in 20 minutes and then kept between 175 and 180 ° C for 2 hours. The mixture was cooled and left overnight, then 200 ml of hydrocarbon solvent were added. The mixture was heated to 130 ° C, filtered through diatomaceous earth and then stripped at 180 ° C bottoms and 2.7 kPa to give 1282 g of product, which contained 5% -4% nitrogen, 2.15% sulfur, 5 , 51% molybdenum and 5.75% oxygen.

Example ΙΣ

To a 1 liter flask were added 400 g of the reaction product of polyisobutenyl chloride, in which the polyisobutene group has a number average molecular weight of 1400, and ethylenediamine in a hydrocarbon solvent. The mixture was stripped and cooled at 160 ° C bottoms and 2.7 kPa to give 289 product, containing 1.58% nitrogen. 200 ml were added to this product.

hydrocarbon thinner, 50 ml water and 296 g MoO4. The mixture was refluxed with stirring, about 101 ° C, boiled for 2 hours and then stripped bottoms at 140 ° C. Then 7 S sulfur was added and the temperature was raised to 155 ° G in 10 minutes and held at this temperature for 30 minutes. The temperature was then raised to 180 ° C in 10 minutes and held at 180 to 185 ° C for 2 hours. The mixture was cooled and 100 ml of hydrocarbon thinner were added. The mixture was then filtered through diatomaceous earth and, after addition of 300 3 2 82 10 100 g of neutral lubricating oil, stripped at 180 DEG C. and 2.7 kPa to yield 409 g of product.

Example X.

To a 1 liter flask was added 290 g of a Hannich-5 base prepared from dodecylphenol, methylamine and formaldehyde and having an alkalinity value of 110 containing 2.7% nitrogen and 200 ml of a hydrocarbon thinner. The mixture was heated to 65 ° C and 50 ml of water and 29 g of molybdenum trioxide were added. The mixture was stirred at reflux, 104 to 110 ° C, for 4.5 hours. The solution turned a bright dark brown color and then stripped bottoms at 175 °. The mixture was cooled to 140 ° C and 7 g of sulfur was added. The temperature was raised to 155 DEG C. in 7 minutes and held at this temperature for 30 minutes. Then the temperature was raised to 180 ° C in 10 minutes and held for 2 hours. The mixture was then cooled and left overnight. The following day, 100 ml of hydrocarbon thinner were added. The mixture was heated to 100 ° C, filtered through diatomaceous earth and then stripped at 180 ° C and 2.7 kPa to yield 3-7 g of product.

Example XI

To a 3 liter flask were added 1160 g of succinimide, as described in Example I, and 800 ml of hydrocarbon thinner. This mixture was heated to 65 ° C and 200 ml of water and 116 g of MoO4 were added. The mixture was refluxed (96 ° G) for 1 hour with stirring. The mixture was cooled and an additional 116 g of 30 MoO4 were added. The mixture was refluxed (97 ° 0) with stirring for 10 hours. The mixture was cooled and left overnight. The mixture was then stripped at 180 ° C, cooled to 140 ° C and 60 g of sulfur were added. Then, the temperature was raised to 155 ° 0 in 15 minutes and held at this temperature for 30 minutes, then leached to 180 ° 0 in 15 minutes and held at this temperature for 3 hours. The mixture was cooled and 200 ml of hydrocarbon thinner were added. The solution was then heated to 130 ° C and filtered through diato-40 co-earth with addition of a hydrocarbon 800 32 82 17 diluent to aid filtration. The filtrate was stripped at 200 ° C and 2.7 kPa to yield 1325 g of product.

Example XII (B-3721-49) To a 1 liter flask was added 400 g of the hydrocarbon polyamine described in Example IX, which was stripped at 160 ° C and 2.7 kPa and then 200 ml of hydrocarbon thinner , 50 ml of water and 29 g of MoO, O 2 are added. The mixture was stirred at 101 ° C for 2 hours and then heated to 140 ° C to remove water. 7 g of Sulfur were added and the temperature was gradually raised to 180-185 ° C, which temperature was maintained for 2 hours. After cooling, 100 ml of hydrocarbon diluent were added and the mixture was filtered through diatomaceous earth and stripped at 180 ° C and 2.7 kPa to yield 409 g of product containing 4.67% molybdenum (neutral activation), 4.93% (X-ray fluorescence); Contains 1.37% oxygen and 1.94% sulfur.

Example XIII

To a 1 liter flask containing 289 g of the stripped polyamine described in Example XII and 200 ml of hydrocarbon thinner at 65 ° C, 50 ml of water and 29 g of MoO were added. The mixture was stirred at reflux for 2 hours and then stripped at 175 ° C.

10 g of H 2 S were added to 25 ha cooling to 110-115 ° C.

The mixture was then heated to 155-160 ° C, which temperature was maintained for one hour. After cooling, 75 ml of hydrocarbon diluent were added and the mixture was filtered through diatomaceous earth. 100 g of neutral oil were added and the mixture was stripped at 180 ° C and 2.7 kPa to yield 412 g of product containing 0.90% nitrogen, 2.31% sulfur, 4.21% molybdenum (neutron activation), 4.67% (X-ray fluorescence) and 1.01% oxygen.

Example XIV

To a 1 liter flask containing 300 g of a borate-treated Mannich base prepared from an alkyl phenol of 80 to 100 carbon atoms, formaldehyde and tetraethylene pentamine or triethylene tetramine, or mixtures thereof containing 40 urea (Amoco 9250) and containing 200 ml of hydrocarbon diluent 800 32 82 ner at 65 ° C, 40 ml of water and 25 g of MoO 2 were added. The mixture was refluxed with stirring for 4.5 N and then stripped at 165 ° C. After cooling to 140 ° C, 7 g of sulfur was added and the temperature was gradually raised to 185 ° C, which temperature was maintained for 2 hours. Then, 75 ml of hydrocarbon diluent were added and the mixture was filtered through diatomaceous earth and then stripped at 180 ° C and 2.7 kPa, yielding 307 g of product, containing 1.04% nitrogen, 2.53% sulfur, 4 68% molybdenum (neutron activation), 4.99% (X-ray fluorescence), 2.53% oxygen and 0.22% boron.

Example XV

To a 3 liter flask were added 500 g of a polyisobutenyl succinic anhydride concentrate, in which the polyisobutenyl group had a number average molecular weight of 980 and 36 g of dimethylaminopropylamine were added. The temperature of the reaction mixture was raised to 160 G, held for one hour and then stripped at 170 ° C and 2.7 kPa. 350 ml of hydrocarbon thinner, 50 ml of water and 29 g of MoO4 were added to this mixture. This mixture was refluxed with stirring for 2 hours and then stripped at 140 ° C to remove water. Then 7 g of sulfur was added and the mixture was kept at 180-185 ° C for 2 hours. After cooling, an additional amount of hydrocarbon diluent was added and the mixture was filtered through diatomaceous earth and then stripped at 180 ° C and 2.7 kPa to yield 336 g of product containing 1.17% nitrogen, 1. Contains 55% sulfur, 3.37% molybdenum (neutron activation), 3% 31% (X-ray fluorescence) and 2.53% oxygen.

Example XVI

To a 1 liter flask containing 290 g of the succinimide described in Example I and 200 ml of hydrocarbon diluent at 65 ° C, 50 ml of water and 29 g of MoO 2 were added. The mixture was refluxed with stirring for 90 minutes and then stripped at 165 ° C to remove water. After cooling to 100 ° C, 40 g of 40-butyl disulfide was added and the mixture was heated to 800 32 82 19 for 2.5 hours.

heated to 180 - 185 ° C. Then an additional 100 ml of hydrocarbon diluent was added before filtration through diatomaceous earth took place and stripped at 180 ° C and 2.7 kPa to give 305 g of product containing 1.90% nitrogen, 0.47 % sulfur, 6.21% molybdenum (neutron activation), 6.34% (X-ray fluorescence), and 4.19% oxygen (neutron activation). Example XVII

To a 1 liter flask containing 290 g of the succinimide described in Example I and 200 ml of hydrocarbon thinner at 75 ° C, 50 ml of water and 29 g of MoO 2 were added. The mixture was refluxed for 90 minutes and then stripped at 200 ° C to remove water. After cooling to 100 ° C, 19 g of thioacet-15 amide was added and the mixture was gradually heated to 200 ° C, which temperature was maintained for 45 minutes. Then, 150 ml of hydrocarbon diluent were added and the mixture was filtered through diatomaceous earth and stripped at 180 ° C and 2.7 kPa to yield a product containing 1.46% nitrogen, 2.05 ° f sulfur, 4.57 ° / ° molybdenum (neutron activation) · * 4.70% (X-ray fluorescence) and contains 2.38% oxygen. This product was diluted with 100 g of neutral lubricating oil before testing. Example XVIII

To 292 g of the starting product described in Example XIII, 200 ml of hydrocarbon thinner, 50 ml of water and 35.5 g of ammonium paramolybdate were added. The mixture was refluxed for 21 hours and then stripped to remove water. After cooling to 140 ° C, 7 g of sulfur were added. The mixture was heated to 180-185 ° C, which temperature was maintained for 2 hours. After addition of 100 ml of hydrocarbon thinner, the mixture was filtered through diatomaceous earth. 100 g of neutral diluent oil were added and the mixture was stripped at 180 ° C and 2.7 kPa to yield 414 g of product containing 0.92% nitrogen, 2.02% sulfur, 4.57% molybdenum (neutron activation), 4.60% (X-ray flurescence) and 1.37% oxygen.

Example XIX

40 To a 3 liter flask containing 1160 g of the succinimide described in Example I and 800 ml of hydrocarbon diluent at 75 ° C, 200 ml of water and 116 g of MoO 2 were added. The mixture was refluxed for 3 hours and then stripped at 180 ° C to remove water. About 64 g was added at 110 ° C. 200 ml of hydrocarbon diluent were added and the mixture was filtered through diatomaceous earth and then stripped at 180 ° C and 2.7 kPa to yield 1290 g of product containing 1.85% nitrogen, 4.24% sulfur, 10 5. Contains 92% molybdenum (neutron activation), 5 »83% (X-ray fluorescence) and 2.12% oxygen.

Example XX

To a 1 liter flask containing 1160 g of the succinimide described in Example I and 800 ml of a hydrocarbon thinner at 75 ° C, 200 ml of water and 116 g of MoO 2 were added. The mixture was refluxed with stirring for 3 hours and then heated to 186 ° C to remove water. After cooling to 110 ° C, 35 g of HgS were added. The mixture was heated to 182 ° C, then 200 ml of hydrocarbon diluent were added and the mixture was filtered through diatomaceous earth. Stripping at 180 ° C and 2.7 kPa gave 1272 g of product containing 1.93% nitrogen, 3.20% sulfur, 5% 90% molybdenum (neutron activation) and 3.01% oxygen.

Example XXI

To a 1 liter flask containing 290 g of the succinimide described in Example I and 200 ml of hydrocarbon thinner at 75 ° C, 50 ml of water and 29 g of MoO 2 were added. The mixture was refluxed with stirring for 90 minutes and then heated to 187 ° C to remove water. Then 100 ml of hydrocarbon thinner were added and 34 g of water containing ammonium polysulfide (31% free sulfur) at 75 ° C. This mixture was slowly heated to 180 ° C and held at this temperature for 2.25 hours. The mixture was then filtered through diatomaceous earth and stripped at 180 ° C and 2.7 kPa to yield 318 g of product containing 1.89% nitrogen, 4.07% sulfur and 6.16% molybdenum (neutron activation). . Example XXII

40 To a 3.1 liter flask containing 290 g of the succinimide described in Example 1 and 200 ml of hydrocarbon diluent at 75 ° C were added 50 ml of water and 29 g of MoO-. This mixture was refluxed for 5 hours and then heated to 195 ° C to remove water. After cooling to 70 ° C, 58 g of a 52-60 pound cent technical solution of ammonium sulfide was added. The reaction mixture was heated to 180 - 185 ° C for 4 hours. After cooling to 115 ° C, 125 ml of hydrocarbon thinner were added, the mixture was filtered through diatomaceous earth and then stripped at 180 ° C and 2.7 kPa to yield 318 g of product containing 6.19% molybdenum (X-ray fluorescence) contains.

Example XXIII

To a 1 liter flask containing 330 g of a concentrate containing 1.50% N in oil of a polyisobutenyl succinimide prepared from triethylene tetramine and a polyisobutenyl succinic anhydride, wherein the polyisobutenyl group has an average molecular weight of 980, and containing 200 ml of hydrocarbon diluent at 75 ° C, 50 ml of water and 22 g of MoO 2 were added. This mixture was refluxed at about 100 ° C for 11 hours with stirring. The mixture was then heated to 180 ° C to remove water. After cooling to 140 ° C, 9 g of sulfur was added and the mixture was slowly heated to 180 ° C, which temperature was maintained for 3 hours. After adding 100 ml of hydrocarbon thinner, the mixture was filtered through diatomaceous earth and then stripped at 180 ° C and 2.7 kPa to yield 34-7 g of product containing 4.13% molybdenum (neutron activation), 3 * 98% (X-ray 30 beam fluorescence), contains 1.42% nitrogen, 2.66% sulfur and 2.85% oxygen (neutron activation).

Example XXIV

To 291 g of the starting product used in Example XIII and 200 ml of hydrocarbon thinner at 75 ° C, 50 ml of water and 29 g of MoO 2 were added. The mixture was refluxed with stirring for 3 hours and then heated to 180 ° C to remove water. After cooling to 140 ° C, 15 g of sulfur was added and the mixture was gradually heated to 180 - 185 ° C, which temperature was maintained for 2.5 hours. After adding 200 ml of o η π 70 0 9 hydrocarbon thinner, the mixture was filtered through diatomaceous earth and then 100 g of neutral diluting oil were added. Stripping at 200 ° C and 2.7 kPa gave 410 g of product containing 4.68% molybdenum (neutron activation).

Example XXV

404 g of polyisobutenyl succinic anhydride, with a PIBSA number of 76.7, were added to a 1 liter flask containing 47 g of tetraethylene pentamine. The mixture was heated to 150-160 ° C, which temperature was maintained for 90 minutes. The mixture was then stripped at 160 ° C and 2.7 kPa to yield 439 g of polyisobutenyl succinimide. 300 ml of hydrocarbon thinner, 135 ml of water and 80 g of MoO4 were added to this succinimide.

The mixture was refluxed for 6.5 hours with stirring and then heated to 140 ° C to remove water. After cooling to 140 ° C, 41 g of sulfur were added and the temperature was gradually raised to 180 - 185 ° C, which temperature was maintained for 4 hours. After adding 200 ml of hydrocarbon thinner, the mixture was filtered through diatomaceous earth and then stripped at 200 ° C and 2.7 kPa and 300 g of neutral oil were added, yielding 810 g of product, which

Contains 6.23% molybdenum by X-ray fluorescence. Example XXVI

To a 1 liter flask containing 290 g of the succinimide described in Example I and 200 ml of hydrocarbon thinner at 75 ° C, 50 ml of water and 29 g of MoO 2 were added. The mixture was stirred at 96-98 ° C for 2.5 hours and then stripped at 191 ° C. After cooling to 75 ° C, 43 ml of 1-butanethiol was added and the mixture was refluxed for 14 hours. The mixture was then stripped at 180 ° C and 2.7 kPa to yield 318 g of product containing 6.17% molybdenum (X-ray fluorescence), 1.97% nitrogen and 1.05% sulfur. Example XXVII

Lubricating oil preparations containing the additives prepared according to the present invention have been tested in various experiments. Listed below are the results of 40 particular runs, which are described as follows.

800 32 82 23 '

In the Oxidator B test, the stability of the oil is measured by the time required for the consumption of 1 liter of oxygen by 100 g of the tested oil at 171 ° C. The actual test uses 25 g of oil and the results are corrected to 100 g samples.

The catalyst used in an amount of 1.38 cm 2 per 100 cm 3 oil contains a mixture of soluble salts, which provide 95 ppm copper, 80 ppm iron, 4.8 ppm manganese, 1100 ppm lead and 49 ppm tin . The results of this test are reported as hours to consumption of 1 liter of oxygen and our measure of the oxidative stability of the oil.

The anti-corrosion properties of preparations can be investigated by their behavior in the CRC L-38 lower corrosion test. In this test, separate strips of copper and lead are immersed in the lubricant to be tested and the lubricant is heated to a temperature of 146 ° C for 20 hours. The copper strip is weighed and then washed with a potassium cyanide solution to remove copper compound deposits. The strip is then weighed again. The weight losses of the two strips are reported as a measure of the degree of corrosion caused by the oil.

The copper strip test is a measure of corrosion against nonferrous metals and has been described as ASM Method D-130. Anti-wear properties are measured according to the 4-ball wear and 4-ball weld tests. The 4-ball seal test is described in ASM D-2266 and is run at 54 ° C for 30 minutes using steel balls and weighing 40 kg and the 4-ball weld test is a variation of ASM D- 2783 performed at ambient temperature to the welding point with weights decreasing by 5 kg until the passage load is determined. The coefficient of friction of an additive-containing lubricating oil of the present invention was examined with the Kinetic Oiliness Testing Machine (KOM) of G.M. Neely of Berkeley, California. The method used in this experiment is described by G.L. Neely, Proceeding of Mid-Year Meeting, American Petroleum Institute 1932, biz. 60-74 and 40 in ASLE Transactions, 8, 1-11 (1965) and AS1E Transactions, 800 32 82] (^ 964) 24-31. The coefficient of friction was measured under limiting conditions at 150 ° C and 204 ° C using a 1 kg load and a molybdenum-filled ring on a cast iron disc. The data for some of these 5 tests conducted on compositions of the present invention are listed in the following table.

Unless otherwise noted, the formulation tested contained a neutral lubricating oil 3 * 5% of a 50 percent concentrate of polyisobutenylsuccinimide, 20mmol / kg sulfur calcium phenate, 30mmol / kg basic magnesium sulfonate, 5 * 5% of a viscosity index improver and 22 mmol / kg product of the present invention. (If necessary, additional succinimide was added to bring the total nitrogen content of the final oil to 2.1%).

800 32 82 25 +5 0 v LA ιΑΟ v Ο Ο (Τ 'Ü ο νβ KWO 00 UD 4 · ΙΆ: Φ>} - ΟΟΟγΟΟΟΟ ο cd οοοοοοοοο Ή «Μ« Η: φ ο υ ra ho Ö> ο Γ- Ο IA0J Ο 00 Ο ιΑ • γοο Κ \ Γ "V OJ CU ν ΙΑΕΝ • Η Ο ν-ντ-ν-ννΟΟ 4» ^ -] ΟΟΟΟΟΟΟΟ Ο γ- r- ΚΛ κλ γγγγγγγ cdr * cöc-OJ xj ν *

r- cd, α cd cd £ i cdcdrQfQcö'aicdOJcdCMrCïtd'STrQO

I OJ'rOJOJ v γγγγγγγγ \ γ \ γγ \ γγ ® ® ® q o n CD · Η · Η · Η

M V V f r — 1 r—! H

O O O

b (1 Φ Φ Φ a r-1 rH i — i LAOl-ACM id- g g g g θΓ1ΛΓ ° 3 3 3 m Φ Φ Φ H ® Ö Ö Ö λ Hl Ö Ö Pi

9 bd -Η -Η -H

& »Θ CUC ^ rAC ^ O \ λ \ ρ va« * #> «» # »r» on on. on * v- <r oo ca lt \ * · · zSOJCvJv'C- ^ "??? Λ φ φ Φ ^ bü & D 60

ij- L0 LA

tA hd 00 M OLAOO lts LALALALA LAlAO -r3 "A) ^ g £ N LD LD LOCS LA LDtAIN ^ LAlDIN · Η · Η · Η g-l OJ v V V V V Ά Ά A V V Ά V 1 ° 1 ° CO I X3 _L3

«Aj q q -P -P -P

il il ί o o o o o o

N N N

.. m h fH

mj Φ φ Φ LD CVI LA CA CU IN IAv LAfA LD O CO 'ti ^ ^ gOJ 0 itii'-chLA IA itcA LA LA it it it ö ö tf

gH (\ J P! r * »··» «·» ··> «» · * O O O

03 I ooooo ooooooo ......

• <yy q oD oO oD

Pi Ö Pi • H * H * rt d d d I «* 'Pt Pi Ö

mm "H · Η * H

• H? & f

+5 η LOr COO ijACOONOCOCAitO HHH

CD® ^. . ». ^ * ·»> «.» ** · * · * · ΦΦΦ dd in OMAST VO CA INCA CO CO ININCNCA j> rj r * • H-dAA-rO- £ £ «Μ · Η ΦΦΦ OS ΦΦΦ H dddf £ ft

ld Η Η Η Η H

H Η Η H HHj_HH> .H O O O

O Φ Η HH Η H |> HHHW 1¾ Η Η M t1 *!> Ggg οφ hhI> hhhH η η hh>>>!> Η Μ Μ Μ Μ Μ Μ Μ Λ Λ>, 0 Η Η Η H i> |> >> Η Μ X Μ Μ Μ Μ Η Μ XW 9 XN Μ W Μ M 'T CLi ΚΛ

ö η n 7 o QO

Claims (16)

1. Process for the preparation of a molybdenum. tend preparation, characterized in that an acidic molybdenum compound, a basic nitrogen compound 5 and a sulfur source for forming a sulfur and molybdenum-containing preparation are combined * 2. Process according to claim 1, characterized in that as basic nitrogen compound a succinimide, carboxylic amide, hydrocarbon polyamines, 10 uses Mannich base, phosphonamide, thiophosphonamide, phosphoramide or viscosity improvers or mixtures thereof. 3. Process according to claim 1 or 2, characterized in that the sulfur source, sulfur, hydrogen sulphide, phosphorus pentasulphide, in which a hydrocarbon residue and x are at least 2, inorganic sulphides or inorganic polysulphides, thioacetamide, thiourea or mercaptans of the formula RSH, wherein R represents a hydrocarbon group or uses a sulfur-containing antioxidant. 4. Process according to claim 3, characterized in that as sulfur source sulfur, hydrogen sulfide, phosphorus pentasulfide, in which B represents a hydrocarbon group with 1 to 4 carbon atoms and x at least 3, inorganic sulfides or inorganic polysulfides, thioacetamide, thiourea or RSH wherein R represents an alkyl group of 1 to 40 carbon atoms and the acidic molybdenum compound used is molybdenumic acid, ammonium molybdate or alkali metal molybdates. 5- Process according to claims 1 to 4, characterized in that the sulfur source is sulfur, hydrogen sulfide, RSH, in which R represents an alkyl group with 1 to 10 carbon atoms, phosphorus pentasulfide or, in which x 'represents at least 1, as acid molybdenum Bond molybdenumic acid or ammonium molybdate and use as succinimide, carboxylic acid amide, hydrocarbon polyamines or Mannich base as basic nitrogen compound. 6. Process according to claims 1 to 5, characterized in that as basic nitrogen compound a hydrocarbon succinimide with 24 to 350 carbon | 800 3 2 82 fabric atoms, a carboxylic acid amide or a Mannich base prepared from an alkyl phenol having 9 to 200 carbon atoms, using formaldehyde and an amine. 7. A method according to claim 6, characterized in that the merPlphasic nitrogen compound uses a polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride and tetraethylene pentamine or triethylene tetramine. 8. Process according to claim 6, characterized in that the basic nitrogen compound used is a carboxylic acid amide prepared from one or more carboxylic acids p of the formula R C00H or a derivative thereof which, after reaction with an amine, gives a carboxylic acid amide, wherein R represents an alkyl group or an alkenyl group containing 12 to 350 carbon atoms and a hydrocarbon polyamine. 9. Process according to claim 8, characterized in that a compound is used in which R represents an alkyl or alkenyl group with 12 to 20 carbon atoms and the hydrocarbon polyamine is tetraethylene pentamine 20 or triethylene tetramine. 10. Process according to claim 5, characterized in that the basic nitrogen compound used is a hydrocarbon polyamine prepared from polyisobutenyl chloride and ethylenediamine, diethylene triamine, triethylene tetramine or tetraethylene pentamine or mixtures thereof. 11. Process according to claim 6, characterized in that the basic nitrogen compound used is a Mannich base prepared from dodecylphenol, formaldehyde and methylamine. 12. Process according to claim 6, characterized in that the basic nitrogen compound used is a Mannich base prepared from an alkyl phenol with 80 to 100 carbon atoms, formaldehyde and triethylene tetramine or tetraethylene pentamine or mixtures thereof. Process according to claims 1 to 12, characterized in that the reaction is carried out in the presence of a polar promoter. 14. A method according to claim 13, characterized in that water is used as the polar promoter. 800 32 82 Lubricating oil preparation, characterized by the presence of an oil of lubricating viscosity and 0.05 to 15% by weight of one or more of the preparations obtained by one or more of the methods of one or more of the preceding claims. Lubricating oil concentrate, characterized by the presence of an oil of lubricating viscosity and or more of the 15 to 90% by weight of a compositions obtained by one or more of the methods of any one of the preceding claims. * * * * * * 800 3 2 82