FR2460324A1 - PROCESS FOR PRODUCING A MOLYBDEN-CONTAINING COMPOUND, PRODUCT OBTAINED, AND LUBRICATING OIL COMPOSITION CONTAINING THE SAME - Google Patents

Abstract

THE INVENTION RELATES TO A PROCESS FOR PRODUCING A COMPOUND CONTAINING MOLYBDENE. THIS PROCESS CONSISTS OF COMBINING AN ACID COMPONENT CONTAINING MOLYBDENE, A COMPOUND CONTAINING BASIC NITROGEN AND A SOURCE OF SULFUR TO FORM A COMPOUND CONTAINING BOTH SULFUR AND MOLYBDENE. APPLICATION AS ANTI-OXIDIZING ADDITIVES FOR LUBRICATING OILS.

Description

The present invention relates to novel

  lubricating oil compositions. It has more particularly

  relates to new lubricating oil compositions.

  which contain, as antioxidants, molybdenum compounds. Molybdenum disulfide has long been a

  advantageous additive for lubricating oil compositions.

  fying. However, one of its main disadvantages is

  its lack of solubility in the oil. Molyb disulfide

  The dene is usually finely ground and then dispersed in the lubricating oil composition to impart friction modifying properties and anti-wear properties to the lubricating oil composition. Finely ground molybdenum disulfide is not an effective oxidative inhibitor in

lubricating oils.

  As an alternative to the fine-particle milling of molybdenum disulfide, several different processes have been tried involving the preparation of molybdenum salts. One type of compound that has been prepared includes molybdenum dithiocarbamates. Representative compositions are described in the US Patent

  No. 3,412,589 which makes known dialkyldi

  thiocarbamates of molybdenum dioxide (VI); in U.S. Patent No. 3,509,051 which discloses sulfated oxymolybdenum dithiocarbamates; and U.S. Patent No. 4,098,705, which teaches sulfur-containing molybdenum dihydrocarbyl dithiocarbamates.

  Another method is to form dithio-

  phosphates instead of dithiocarbamates. Examples

  Examples of this type of molybdenum compound include the compounds disclosed in U.S. Patent No. 3,494,866, such as oxymolybdenum diisopropylphosphorodithioate. U.S. Patent No. 3,184,410

  describes certain acetylacetonates of dithiomolybdenyl

  born to be used in lubricating oils.

  2. Braithwaite and Greene describe in Wear, 46 (1978), 405-432 various compounds containing molybdenum,

  intended for use in motor oils.

  U.S. Patent 3,349,108 teaches a complex of molybdenum trioxide with diethylenetriamine for use as an additive for

molten steel.

  The patent of the U.R.S.S. 533 625 teaches

  lubricating oil additives prepared from molyb-

  date of ammonium and alkenyl polyamines.

  Another method of incorporating molybdenum compounds into an oil is to prepare a colloidal complex of disulphide or molybdenum oxysulfides in dispersion using known dispersants. U.S. Patent No. 3,223,625 discloses a process in which an acidic aqueous solution of certain

  Molybdenum is prepared and extracted with a hydro-

  carbon dioxide dispersed by means of a dispersing agent soluble in

  the oil, then freed from the ether. The United States Patent

  United States No. 3,281,355 teaches the preparation of a molybdenum disulfide dispersion by forming a mixture of lubricating oil, dispersing agent and a molybdenum compound in water or in an aliphatic alcohol. C1 to C4, bringing the mixture into contact with a sulphide ion generator, and then removing the solvent. Dispersants

  considered effective in this process are sulpho

  petroleum naphtha, phenates, alkylphenate sulphides,

  phosphosulfurized olefins and mixtures thereof.

  We have just discovered that a lubricating oil additive can be prepared by combining an acidic molybdenum compound, a basic compound containing nitrogen, preferably in the presence of a polar activator and a source of sulfur to form a complex containing molybdenum and

sulfur.

  Lubricating oil compositions containing the additive prepared as described herein are effective in the fluid state and in the grease state (depending on the particular additive or additives that are used) to inhibit. oxidation, provide anti-wear and extreme-pressure properties and / or modify the friction properties of the oil, so that when the oil is used as a crankcase lubricant, it can reduce fuel consumption . The precise molecular formula of the molybdenum compounds of the present invention is not known with certainty; however, it is assumed that these are

  in which the molybdenum, whose valencies are satis-

  made by oxygen or sulfur atoms, is either complexed with the basic nitrogen-containing compound, or the salt of one or more nitrogen atoms of that compound, used

  in the preparation of said compositions.

  The molybdenum compounds used to prepare the compositions of the invention are acidic compounds. We

  means by the term acid that molyb-

  dene react with a basic nitrogen compound, as can be

  measure by ASTM D-664 or D-2896 titration method.

  Normally, these molybdenum compounds are hexavalent and

  are represented by the following compounds: molyb-

  dique, ammonium molybdate, sodium molybdate, molybdate.

  potassium and molybdate other alkali metals and other molybdenum salts such as acidic salts, for example sodium molybdate, MoOCl4, MoO2Br2, M0203C16, molybdenum trioxide or similar molybdenum acid compounds. The preferred molybdenum acid compounds are molybdic acid, ammonium molybdate and alkali metal molybdates. We particularly appreciate

  molybdic acid and ammonium molybdate.

  301 The basic nitrogen compound must have a content

  in basic nitrogen that can be measured by ASTM D-

  664 or D-2896. It is preferably soluble in oil. Representative examples of these compounds include

  succinimides, amides of carboxylic acids, hydro-

  carbylmonoamines, hydrocarbon polyamines, Mannich bases, phosphonamides, thiophosphonamides, phosphoramides, dispersant viscosity index improvers, and mixtures thereof. These basic nitrogen-containing compounds are described below (it should be remembered that each of them must have at least one basic nitrogen atom). Any of the nitrogen-containing compounds may be post-treated with, for example, boron by methods well known in the art, provided that the compounds continue to contain basic nitrogen. These post-treatments are applicable in

  particularly succinimides and Mannich bases.

  The monosuccinimides and polysuccinimides that can be used to prepare lubricating oil additives described herein are set forth in many references and are well known in the art. Certain basic types of succinimides and related materials covered by the term "succinimideu" are described in U.S. Patent Nos. 3,219,666, 3,172,892 and 3,272,746. The term "succinimide" refers in the US Pat. practice of many amides, imides and amidines which are also formed by this

  reaction. However, the predominant product is a succinate

  imide and this term has been broadly adopted to refer to the product of a reaction of an alkenyl-substituted succinic acid or an anhydride of such an acid with a nitrogen-containing compound. Succinimides that are appreciated because they are commercially available

  are succinimides prepared from a hydro-

  carbyl succinic whose hydrocarbyl group contains about 24 to about 350 carbon atoms, and an ethylenic amine, the ethylenic amines being illustrated in particular by ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Succinimides prepared from polyisobutenyl succinic anhydride having 70 to 128 atoms are particularly preferred.

  carbon and tetraethylenepentamine or triethylene-

tetramine or their mixtures.

  The term succinimide also covers co-

  oligomers of a hydrocarbyl succinic acid or anhydride thereof and a secondary polyamine containing at least one tertiary amine atom in addition to two or more secondary amino groups. Ordinarily, this compound has a

  average molecular weight of 1500 to 50 000. An example

  Such a compound would be the compound prepared by reacting polyisobutenyl succinic anhydride with ethylenedipiperazine. Compounds of this kind are described

  in U.S. Patent No. 816,063.

  Carboxylic amides are also advantageous starting materials for use in preparing the products of the invention. Representative examples of these compounds are described in US Pat. No. 3,405,064. These compounds are ordinarily

  prepared by reaction of a carboxylic acid or anhy-

  or an ester thereof, having at least about 12 to about 350 aliphatic carbon atoms in the chain

  aliphatic principle and, where appropriate, a sufficient number

  of lateral aliphatic groups to render the molecule

  soluble in the oil, with an amine or a hydrocarbyl-

  polyamine, for example an ethylene-amine, to form a mono- or polycarboxylic acid amide. Amides prepared from (1) of a carboxylic acid of the formula R 2 COOH, where R 2 is a C 12 alkyl group, are preferred.

  C20 or a mixture of this acid with a polyiso-

  butenylcarboxylic group whose polyisobutenyl group contains 72 to 128 carbon atoms and (2) an ethylenic amine,

  especially triethylenetetramine or tetraethylene

pentamine or mixtures thereof.

  Another class of compounds that we can

  use according to the invention comprises hydro-

  carbylpolyamines, preferably of the type described in the patent

  United States of America No. 3,574,576.

  carbyl, which is preferably an alkyl group or an olefinic group having one or two sites of unsaturation, usually contains from 9 to 350, preferably from 20 to 200 carbon atoms.

  carbon. Hydrocarbyl polyols are particularly preferred.

  amines which are obtained for example by reaction of polyisobutenyl chloride and a polyalkylenepolyamine such as ethyleneamine, for example ethylenediamine,

  diethylenetriamine, tetraethylenepentamine, 2-amino

6.

  ethylpiperazine, 1,3-propylenediamine, 1,2-propylene-

diamine, etc.

  Another class of compounds providing useful

  Basic nitrogen comprises Mannich bases. These compounds are prepared from a C 9 -C 20 phenol or alkylphenol, an aldehyde such as formaldehyde or a formaldehyde precursor, such as paraformaldehyde, and an amine. The amine may be a monoamine or a polyamine and characteristic compounds are prepared from an alkylamine such as methylamine or a

  ethylene amine such as diethylenetriamine or tetra-

  ethylenepentamine, etc. The phenolic material may be sulfurized and is preferably dodecylphenol or a C80 to C100 alkylphenol. Examples of the Mannich base which can be used in the process of the invention are the bases described in United States Patent Application No. 838,197, filed September 30, 1977, and in United States Patents. No. 3,649,229, Nos. 3,368,972 and 3,539,663. The latter patent discloses Mannich bases prepared by reaction of an alkylphenol having at least 50 carbon atoms, preferably 50 to

  carbon atoms with formaldehyde and an alkylene-

  polyamine HN (ANH) nH wherein A is a saturated divalent alkyl radical having 2 to 6 carbon atoms and n is 1 to 10 and the condensation product of said alkylene polyamine may be further reacted with the urea or thiourea. The value of these Mannich bases as starting materials for the preparation of lubricating oil additives can often be significantly improved by treatment of the Mannich base by conventional methods.

  to introduce boron into the compound.

  Another class of compounds useful for the preparation of the additives of the invention include phosphoramides and phosphonamides such as those described in U.S. Patent Nos. 3,909,430 and 3,968,157. compounds by forming a phosphorus compound having at least one

  P-N. They can be obtained for example by reaction of oxy-

  7. Phosphorus chloride with a hydrocarbyl diol in the presence of a monoamine or by reaction of phosphorus oxychloride

  with a difunctional secondary amine and a monoamine amine

  functional. Thiophosphoramides can be prepared by reacting an unsaturated hydrocarbon compound containing 2

  at 450 or more than 450 carbon atoms, such as poly-

  ethylene, polyisobutylene, polypropylene, ethylene, 1-

  hexene, 1,3-hexadiene, isobutylene, 4-methyl-1-pentene, etc., with phosphorus pentasulfide and a nitrogen-containing compound as defined above, especially an alkylamine, an alkyl diamine, an alkylpolyamine or a

  alkylene amine such as ethylenediamine, diethylene glycol

  triamine, triethylenetetramine, tetraethylene

  pentamine, etc. Another class of nitrogen-containing compounds that can be used in the preparation of the molybdenum compounds of the invention include the viscosity index (IV) improvers of the dispersants. Viscosity index improvers are usually

  prepared by functionalization of a hydro-

  carbide, in particular a polymer derived from ethylene and / or propylene, optionally containing additional units derived from one or more comonomers such as olefins

  or alicyclic or aliphatic diolefins. Function-

  may be carried out by various processes which introduce

  on the polymer one or more reactive sites having usually at least one oxygen atom. The polymer is

  then put in contact with a nitrogen source in order to introduce

  functional groups containing nitrogen on the

  main chain of the polymer. Typical nitrogen sources

  Also included are any basic nitrogen compounds, including the nitrogen compounds and compositions disclosed herein. Preferred sources of nitrogen are

  alkylene amines such as ethylene amines, alkyl

amines and Mannich bases.

  Basic nitrogen compounds which are preferred for use in the present invention are

  succinimides, carboxylic acid amides

and Mannich bases.

  Examples of sulfur sources include sulfur itself, hydrogen sulfide, sulfur monochloride, sulfur dichloride, phosphorus pentasulfide, a compound of the formula R2Sx wherein R is a hydrocarbyl radical, preferably a C1 to C40 alkyl radical and x is at least 2, inorganic sulfides and polysulfides such that (NH4) 2Sx ox is at least 1, thioacetamide, thiourea and mercaptans of formula RSH

  in which R has the definition given above.

  It is also possible to use sulphurants

  conventional sulfur-containing antioxidants such as wax sulfides and polysulfides, sulfurized olefins, sulfurized carboxylic acids and their esters, sulfurized olefinic esters and sulfurized alkylphenols

as well as their metal salts.

  The sulfur-containing fatty acid esters are prepared by reacting sulfur, sulfur monochloride and / or sulfur dichloride with an unsaturated fatty acid ester,

  high temperatures. Representative esters include

  C1 to C20 alkyl esters of unsaturated C8 to C24 fatty acids such as palmitoleic, oleic, ricinoleic, petroselinic, vaccenic, linoleic,

  linolenic, oleostearic, licanic, paranaric, tartaricidal,

  rica, gadoleic, arachidonic, cetoleic, etc. Particularly advantageous results have been obtained with mixed unsaturated fatty acid esters such as those derived from animal fats and vegetable oils, for example tall oil, linseed oil, olive oil, castor oil, peanut oil, rapeseed oil, fish oil, spermaceti oil, etc. Examples of fatty esters include lauryl tallate, methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate, lauryl ricinoleate, linoleate. 'oleyl, the

  oleyl stearate and alkylglycerides.

  It is also possible to use cross-sulfurized mixtures of esters and olefins, for example a sulfuric mixture of C 10 to C 25 olefins with C 10 to C 25 fatty acid esters and alkyl or alkenyl alcohols. C1 to

  C25, the fatty acid and / or the alcohol being unsaturated.

  Sulphurized olefins are prepared by reacting

  of the C3 to C6 olefin or a low molecular weight polyolefin derived therefrom with a sulfur-containing compound, such as elemental sulfur, monochloride,

  sulfur and / or sulfur dichloride.

  Aromatic sulphides and alkyl sulphides such as dibenzyl sulphide, dixylyl sulphide, dicetyl sulphide, sulphide and polysulfide of two paraffinic wax molecules, cracking products of a wax and an olefin, etc. can also be used. They can be prepared by treatment of the starting material, for example, olefinically unsaturated compounds, with sulfur, monochloride of

  sulfur and sulfur dichloride. We particularly appreciate

  The paraffinic wax thiomers described in

  U.S. Patent No. 2,346,156.

  Sulfurized alkylphenols and their metal salts

  These include compounds such as dodecylphenol sulfide 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,

  especially sodium salt, calcium, magnesium or barium.

  Preferred sources of sulfur include elemental sulfur, hydrogen sulfide, phosphorus pentasulfide, products of formula R 2 S, wherein R is a hydrocarbyl radical, preferably a C 1 -C 10 alkyl radical, and x is at least equal to 3, mercaptans wherein R is a C1-C10 alkyl group, inorganic sulfides and polysulfides, thioacetamide and thiourea. The

  The most popular sources of sulfur are sulfur

  sulphuretted hydrogen, phosphorus pentasulphide and

  inorganic sulfides and polysulfides.

  The polar activator which is used preferentially

  In the process of the invention is an activator which facilitates the interaction between the molybdenum acid compound and the basic nitrogen compound. Very varied examples of these

  activators are well known to those skilled in the art. Activities

  Representative solvents include 1,3-propanediol, 1,4-butanediol, diethylene glycol, butyl cellosolve, propylene glycol, 1,4-butylene glycol, methyl carbitol,

  ethanolamine, diethanolamine, N-methyldiethanol-

  amine, dimethylformamide, N-methylacetamide, dimethylacetamide, methanol, ethylene glycol,

  dimethylsulfoxide, hexamethylphosphoramide, tetrahydro-

  furan and water. We give preference to water and

  ethylene glycol. We particularly appreciate water.

  Although the polar activator is usually added separately to the reaction mixture, it can often be present, particularly in the case of water, as a component of non-anhydrous starting materials or as a water of hydration in the acidic compound. molybdenum, for example (NH4) 6Mo7024.4H2O. Water can be added also under

the form of ammonium hydroxide.

  A process for preparing compounds of the

  The present invention consists in forming a precursor solution

  Molybdenum acid and a basic nitrogen-containing compound, preferably in the presence of a polar activator, with or without a diluent. The diluent is used as needed to adjust a suitable viscosity for agitation

  Easy. Examples of diluents include lubricating oils.

  and liquid compounds containing only carbon and hydrogen. If desired, ammonium hydroxide can also be added to the reaction mixture to form an ammonium molybdate solution. This reaction is conducted at a temperature from the melting point of the mixture to the reflux temperature. It is usually conducted at atmospheric pressure, although higher or lower pressures may be used where appropriate. This reaction mixture is treated with a sulfur source, as

  defined above, at a suitable pressure and temperature

  the sulfur source reacts with the acidic molybdenum compound and the basic nitrogen-containing compound. In some cases, removal of water from the reaction mixture may be desirable before completion of the reaction.

reaction with the source of sulfur.

  i1. In the reaction mixture, the ratio of the molybdenum compound to the basic nitrogen compound is not

  determining; however, as the amount of molyb-

  dene increases with respect to the basic nitrogen, the filtration of the product becomes more difficult. Since the molybdenum compound is likely to undergo oligomerization, it is advantageous to add as much molybdenum as can easily be maintained in the composition. Ordinarily, the reaction mixture is supplemented with 0.01 to 2.00 molybdenum atoms per basic nitrogen atom. 0.4 to 1.0 and in particular 0.4 to 0.4 are preferably added to the reaction mixture.

  0.7 molybdenum atom per basic nitrogen atom.

  The source of sulfur is usually introduced

  in the reaction mixture in a ratio selected so that there is 0.1 to 4.0 sulfur atoms per molybdenum atom. 0.5 to 3.0 sulfur atoms per molybdenum atom and in particular 1.0 to 2.6 carbon atoms are preferably added.

sulfur per molybdenum atom.

  The polar activator, which is used if

  and preferably, is usually present in proportion

  0.1 to 50 moles of activator per mole of molybdenum. Preferably, there is 0.5 to 25 and especially 1.0 to 15 moles

  of activator per mole of molybdenum.

  Lubricating oil compositions containing the additives of the invention may be prepared by mixing, by conventional operations, the appropriate amount of molybdenum-containing compound with a lubricating oil. The choice of particular base oil depends on the application for which the lubricant is intended and the presence of other additives. Generally, the amount of additive containing molybdenum varies from 0.05 to 15% by

  weight and preferably from 0.2 to 10% by weight.

  The lubricating oil that can be used in accordance with the invention comprises a wide variety of hydrocarbon oils such as naphthenic bases, paraffinic bases and mixed base oils as well as synthetic oils such as esters, etc. Lubricating oils can be used individually 12.

  or in combination and their Saybolt viscosity is generally

  in the range of 50 to 5000 universal seconds, and

  usually from 100 to 15,000 universal seconds at 380C.

  In many cases it may be advantageous to form concentrates of the molybdenum-containing additive in a liquid vehicle. These concentrates are a convenient way of handling and transporting the additives before

  their dilution and subsequent use. The concentration

  of the additive containing molybdenum in the concentrate

  can vary from 0.25 to 90% by weight, although it is preferred

  maintain a concentration of 1 to 50% by weight.

  The final application of the lubricating oil compositions of the invention can reside in lubricants for marine cylinders, for example in diesel engines with a spacer,

  crankcase lubricants, for example in vehicles

  automotive and railway components, lubricants for

  heavy industry, for example steel mills

  etc., or as bearing greases, etc. The

  The fluid or solid content of the lubricant usually depends on the presence of a thickening agent. Examples of thickeners include polyurea acetates, lithium stearate, and the like. Where appropriate, other additives may be

  included in the lubricating oil compositions of the invention

  tion. These additives include antioxidants or oxidation inhibitors, dispersants, rust inhibitors, anti-corrosion agents, and the like. Anti-foaming agents, stabilizers, antifoulants, tackifiers, anti-knock agents, drop-point improvers, anti-squeaks, extreme pressure, deodorizing agents, etc. Some molybdenum products that can be prepared by the process of the invention can also be used in the production of brake linings, in

  building materials resistant to high temperatures

  in iron and steel alloys, in

  sheathing materials, in electro-

  13. Deposition, as components for electrodes for

  electric discharge machines, as fuel additives

  or fuels, in the production of self-supporting

  lubricants or wear-resistant agents, as

  in processes for the phosphatization of steel, in solder fluxes, in nutrient media for microorganisms, in the production of an electrically sensitive recording medium, in refining catalysts coal, oil,

  shale, tar sands, etc., or as stabilizing agents

  leaflets or vulcanizing agents of natural rubber or

polymers.

  The implementation of the invention is illustrated

  by the following examples, given in a non-limiting manner.

EXENT 1

  290 g of a solution of 45% concentrate in succinimide oil prepared from polyisobutenyl succinic anhydride and tetraethylene pentamine and having a number average molecular weight for the group are charged into a 500 ml flask. polyisobutenyl of about 980, and 150 ml of hydrocarbon diluent. The mixture is heated to 1200C. A solution containing 28.8 g of molybdenum trioxide in 12.9 g of concentrated ammonium hydroxide diluted to 100 ml with water (0.21 mole) is then added over a period of 45 minutes at 100-110 ° C. ammonia). The reaction mixture is heated to reflux (about 1550C) and maintained at this temperature for 1 hour. Hydrogen sulfide is added at 115 ° C. A total of 10 g of hydrogen sulphide is added, and the reaction mixture is then purged with nitrogen for 1 hour at 11 ° C. The mixture is then heated to 1550C and maintained at that temperature for 1 hour. 100 ml of hydrocarbon diluent is added to the mixture, and the mixture is then filtered while hot on diatomaceous earth. The product is distilled at 1600C under a vacuum of 2.63 kPa to obtain 316.6 g of product containing 4.94% molybdenum, 2.77% oxygen,

2.10% sulfur and 1.91% nitrogen.

14.

EXAMPLE 2

  It is added drop by drop in 45 minutes at 100-

   A solution of 28.8 g of molybdenum trioxide in

  0.2 mole of ammonia contained in 12.9 ml of ammonium hydroxide

  The reaction mixture is heated to a solution of 290 g of the succinimide defined in Example 1. The reaction mixture is heated to reflux at about 1550C and maintained at this temperature for 1 hour. The mixture is then heated to 1400C and 4 g of sulfur are added thereto. The temperature is raised to reflux at 1550C and maintained at this value for 1 hour. The temperature is then raised to 165-170 ° C. and maintained in this range for 2 hours. 100 ml of hot hydrocarbon diluent is then added to the mixture to obtain about 200 ml of solvent in the reaction flask. The mixture is filtered while hot on diatomaceous earth and then distilled at 1600C under a vacuum of 2.63 kPa to obtain 312.8 g of product containing 5.39% molybdenum, 1.75%

  nitrogen, 3.50% oxygen and 1.30% sulfur.

EEMPLE 3

  290 g of the succinimide described in Example 1 and 150 ml of hydrocarbon diluent are charged into a 1-liter flask. The reaction mixture is heated to 65 ° C. and 28.8 g of molybdenum trioxide and 50 ml of water are added thereto. The temperature is maintained at 65-701C for half an hour, then raised to 1500C. After 50 minutes at 1500C, we

  add 5 g of elemental sulfur and 50 ml of hydrogen diluent

  carbon. The temperature is raised to 155-160 ° C (reflux) over a period of half an hour. A little solvent is removed and the temperature is raised to 165-1700C. The mixture is maintained at this temperature for 2 hours. Ml of hydrocarbon diluent is added to the mixture and the mixture is filtered through diatomaceous earth and then distilled at 1600 ° C. under a vacuum of 2.63 kPa to obtain 314.5 g of product containing 4.93 molybdenum, 3, 53% oxygen, 1.92% nitrogen and

1.49% sulfur.

15.

EXAMPLE 4

  290 g of succinimide described in Example 1 and 150 ml of hydrocarbon diluent are charged into a 1-liter flask. The mixture is heated to 65 ° C. and 28.8 g of molybdenum trioxide and 50 ml of water are added thereto. The temperature is maintained at 65 ° C. for half an hour and is raised to WC in a period of 55 minutes. 7 g of elemental sulfur and 100 ml of hydrocarbon diluent are added to the mixture. The reaction mixture is maintained at reflux temperature at

  about 1551C for 45 minutes, then raise the temperature

  at 165-1700C and maintained at this value for 2 hours. 50 ml of hydrocarbon diluent are added to the mixture and the reaction mixture is filtered while hot on diatomaceous earth. The filtrate is distilled at 160 ° C. under a vacuum of 2.63 kPa to obtain 316.5 g of product containing 6.35% of molybdenum, 3.57% of oxygen, 1.86% of nitrogen and 2.15% of nitrogen. of sulfur.

EXAMPLE 5

  290 g of the succinimide described in Example 1, 28.2 g of molybdenum trioxide, 50 ml of water and 150 ml of hydrocarbon diluent are charged into a 1-liter flask. We

  heat the mixture to 650C and maintain it at this temperature.

  for half an hour. 6 g of hydro-

  sulfide gene at 63-651C for a period of 15 minutes.

  After the addition, the temperature is maintained at 63-65 ° C for 1 hour with vigorous stirring under a nitrogen atmosphere. The temperature is then raised to 1000C to drive off most of the water, then to 155160WC, and the mixture is refluxed for 1 hour. It is hot-filtered on diatomaceous earth and then distilled at 160 ° C. under a pressure of 2.63 kPa to obtain 314.15 g of product containing 5.87% of molybdenum and 3.64% of oxygen. , 05%

  nitrogen, 0.75% sulfur and 0.08% sediment.

EXAMPLE 6

  290 g of the succinimide described in Example 1 and 150 ml of hydrocarbon diluent are charged into a 1-liter flask. The reaction mixture is heated to 65 ° C. and 28.8 g of molybdenum trioxide and 50 ml of water are added thereto. We keep the temperature at 650C for half an hour and we

  raise it slowly to 1200C, then add 10g of sulfur

  mentary. The temperature is raised to 1550C, and maintained at this value for 30 minutes, at 1600C for 15 minutes, 1700C for 30 minutes, 1750C for 30 minutes and 1800C for 30 minutes. 120 ml of hydrocarbon diluent are then added and the reaction mixture is filtered through diatomaceous earth and the filtrate is then distilled at 1600 ° C. under a pressure of 2.63 kPa to obtain a product containing 5.70 molybdenum, 2.88 %

  of oxygen, 1.83% of nitrogen and 2.94% of sulfur.

EXAMPLE 7

  1160 g of succinimide described in Example 1 and 800 ml of hydrocarbon diluent are charged into a 3-liter flask. The reaction mixture is heated to 65 ° C. and 200 ml of water and 116 g of MoO 3 are added thereto. The mixture is heated to reflux temperature (98 ° C) and maintained at this temperature for 2.5 hours until the solution turns a light green tint. The water is flushed until the tails have reached a temperature of

  1400C. 60 g of sulfur are then added. We raise the temperature

  at 1551C in a period of 15 minutes and maintained at this value for half an hour. The temperature is then raised to 1800 ° C. over a period of 30 minutes and this temperature is maintained for 3.5 hours. The mixture is then cooled and allowed to stand for about 18 hours. Then 200 ml of diluent consisting of a hydrocarbon solvent is added and the solution is heated to 1300C. It is then filtered through diatomaceous earth and distilled at 2000 ° C. under a pressure of 2.63 kPa to obtain 1287 g of product containing 4.49% of sulfur, 82% of molybdenum and 2.58% of oxygen. .

EXAMPLE 8

1160 g of a polyamide prepared from a C18 and 17 carboxylic acid tetraethylene pentamine and containing 6.29% of nitrogen and 800 ml of hydrocarbon diluent are charged into a 3-liter flask. The mixture is heated to 65 ° C. and 200 ml of water and 116 g of MoO 3 are added. The temperature is raised to reflux, i.e., about 950C, and the mixture is held at this temperature for 4 hours until the solution becomes light green. The solvent is removed at a maximum temperature of 150 ° C., and then

  the mixture is cooled to 1400C and 28 g of sulfur are added.

  The temperature is raised to 1550C in a period of 15 minutes and maintained at this value for half an hour. The temperature is raised again to 1750C in a period of minutes, then maintained at 175-180 ° C. for 2 hours. The mixture is cooled and allowed to stand for about 18 hours and then 200 ml of hydrocarbon solvent is added. The mixture is heated to 1300C, filtered through

  diatomaceous earth, then distilled at a temperature of

  tails of 1800C at a pressure of 2.63 kPa to obtain 1282 g of product containing 5.45% of nitrogen, 2.15% of

  sulfur, 5.51% molybdenum and 5.73% oxygen.

EXEPLE 9

  400 g of the reaction product are charged into a 1-liter flask between a polyisobutenyl chloride whose polyisobutene group has a number average molecular weight of 1400 and ethylenediamine in a hydrocarbon solvent. The mixture is distilled at a bottom temperature of 1600 ° C. under a pressure of 2.63 kPa and cooled to obtain 289 g of product containing 1.58% nitrogen. 200 ml of hydrocarbon diluent, 50 ml of water and 29 g of MoO 3 are added to this product. The mixture is stirred under reflux at about 10 ° C. for 2 hours and then distilled to a tails temperature of 140 ° C. 7 g of sulfur are then added and the temperature is raised to 1550 ° C. in a period of minutes and maintained at this value for half an hour. The temperature is then raised to 1800C over a period of 10 minutes and maintained at 180-1850C for 2 hours. The mixture is cooled and 100 ml of hydrocarbon diluent is added thereto. The mixture is then filtered through diatomaceous earth and, after adding 100 g of neutral lubricating oil, is distilled at a quill temperature of 180 ° C. at a pressure of 2.63 kPa to obtain 409 g.

of product.

EXAMPLE 10

  290 g of a Mannich base prepared from dodecylphenol, of methylamine and of formaldehyde having an alkalinity number of 110 and containing 2.7% of nitrogen are charged into a 1-liter flask and 200 ml of a hydrocarbon diluent. The mixture is heated to 650 ° C. and ml of water and 29 g of molybdenum trioxide are added thereto. The mixture is stirred at reflux (104-1100 ° C.) for 4½ hours. The clear solution turns dark brown in color and is distilled at 1751C tails. The mixture is allowed to cool to 1400C and 7 g of sulfur are added. The temperature is raised to 1551C in a period of

  7 minutes and hold at this value for one half

  hour. The temperature is then raised to 1800C over a period of 10 minutes and held there for 2 hours. The mixture is then allowed to cool and allowed to stand for half an hour. The next day, 100 ml of hydrocarbon solvent is added. The mixture is heated to 1000C and filtered through diatomaceous earth and distilled at 180 ° C.

  under pressure of 2.63 kPa to obtain 317 g of product.

EXAMPLE 11

  1160 g of succinimide as described in Example 1 and 800 ml of a hydrocarbon diluent are charged into a 3-liter flask. This mixture is heated to 650 ° C. and 200 ml of water and 116 g of MoO 3 are added thereto. The mixture was stirred at reflux (960C) for 2 hours. It is cooled and another 116 g of MoO 3 are added. This mixture is stirred at reflux (970C) for 10 hours. The mixture is cooled and allowed to stand for about 18 hours. It is then distilled at 180 ° C., cooled to 140 ° C. and 60 g of sulfur are added thereto. The temperature is then raised to 1550C over a period of 15 minutes and maintained at this value for one-half hour, then heated to 1800C over a period of 15 minutes and maintained at that temperature for 3 hours. Cool the mixture and add

  ml of hydrocarbon diluent. The solution is then heated

  at 1300C and is filtered through diatomaceous earth

  adding a hydrocarbon diluent to facilitate filtration

  tion. The filtrate is distilled at 2000 ° C. under

  2.63 kPa to obtain 1325 g of product.

EXAMPLE 12 (B-3721-49)

  400 g of the hydrocarbylpolyamine described in Example 9, which is distilled at 160 ° C. under a pressure of 2.63 kPa, are then charged into a 1-liter flask and then added

  ml of hydrocarbon diluent, 50 ml of water and 29 g of MoO3.

  The mixture is stirred at 10 ° C. for 2 hours and then heated at 14 ° C. to drive off the water. 7 g of sulfur are added and the temperature is gradually raised to 180-185 ° C. and maintained at this value for 2 hours. After cooling, 100 ml of hydrocarbon diluent is added and the mixture is filtered through diatomaceous earth and then distilled at 180 ° C. under a pressure of 2.63 kPa to obtain 409 g.

  of product containing molybdenum (4.67% according to the

  neutron ionization, 4.93% according to the fluorescence

  X), 1.37% oxygen and 1.94% sulfur.

EXAMPLE 13

  50 ml of water and 29 g of MoO3 are charged into a 1-liter flask containing, at 650 ° C., 289 g of the polyamine.

  rectified from Example 12 and 200 ml of hydrocarbon diluent.

  The mixture is stirred at reflux for 2 hours and then distilled at 1750C. After cooling to 110-115 ° C., 10 g of hydrogen sulphide are added. The mixture is then heated to 155-160 ° C and maintained at this temperature for 1 hour. After cooling, 75 ml of hydrocarbon diluent is added and the mixture is filtered through diatomaceous earth. 100 g of neutral oil are added and the mixture is distilled at 1800 ° C. under a pressure of 2.63 kPa to give 412 g of product containing 0.90% of nitrogen, 2.31% of sulfur, 20. 4.21% (neutron activation) or 4, 67% (fluorescence at

  X-rays) of molybdenum and 1.01% oxygen.

EXAMPLE 14

  It is loaded into a 1-liter flask containing 300 g of borated Mannich base prepared from a

  C80 to C100 alkylphenol, formaldehyde and tetra-

  ethylenepentamine or triethylenetetramine or their mixtures and containing urea ("Amoco 9250") and 200 ml of hydrocarbon diluent at 650C, 40 ml of water and 25 g of MoO3. The mixture is stirred under reflux for 4 hours and then distilled at 165 ° C. After cooling to 140 ° C., 7 g of sulfur are added and the temperature is gradually raised to C, at which point it is maintained for 2 hours. . 75 ml of hydrocarbon diluent are then added and the mixture is filtered on diatomaceous earth and then distilled at a pressure of 2.63 kPa C to obtain 307 g of product.

  containing 1.04% nitrogen, 2.53% sulfur, 4.68%

  neutron count) or 4.99% (X-ray fluorescence) of

  molybdenum, 2.53% oxygen and 0.22% boron.

EXAMPLE 15

  500 g of a polyisobutenyl succinic anhydride concentrate whose polyisobutenyl group has a weight average number are charged into a 3-liter flask.

  molecular weight of about 980 and 36 g of dimethylaminopropyl-

  amine. The temperature of the reaction mixture is raised to 1600 ° C., maintained at this value for 1 hour, and then the mixture is distilled at 170 ° C. under a pressure of 2.63 kPa. 350 ml of hydrocarbon diluent, 50 ml of water and 29 g of MoO 3 are added to this mixture. The mixture is stirred under reflux for 2 hours and then distilled at 140 ° C. to remove the water. 7 g of sulfur are then added and the mixture is kept at

  -185 C for 2 hours. After cooling, we introduce

  an additional quantity of hydrocarbon diluent is added and the mixture is filtered through diatomaceous earth and then distilled at 180 ° C. under a pressure of 2.63 kPa to obtain 336 g of product containing 1.17% of nitrogen, 1, 55% sulfur, 3.37% 21. (neutron activation) or 3.31% (ray fluorescence

  X) molybdenum and 2.53% oxygen.

EXAMPLE 16

  It is charged into a 1-liter flask containing 290 g of the succinimide described in Example 1 and 200 ml of hydrocarbon diluent at 65 ° C., 50 ml of water and 29 g of MoO3. The mixture is stirred under reflux for 1.5 hours and then distilled at 165 ° C to remove the water. After cooling to 100 ° C., 40 g of butyl disulphide are added and the mixture is heated.

  the mixture at 180-185 C for 2.5 hours. We introduce

  then added an additional 100 ml of hydrocarbon diluent before filtering on diatomaceous earth and distilled at 180 ° C. under a pressure of 2.63 kPa to obtain 305 g of product containing 1.90% of nitrogen, 0, 47% sulfur, 6.21% (neutron activation) or 6.34% (X-ray fluorescence) of molybdenum and 4.19% (neutron activation) of oxygen.

EXAMPLE 17

  50 ml of water and 29 g of MoO 3 are charged into a 1-liter flask containing 290 g of the succinimide described in Example 1 and 200 ml of C-hydrocarbon diluent. The mixture is refluxed for 1 hour and a half. ,

  then distilled at 200 C to flush the water. After cooling

  At 100 ° C., 19 g of thioacetamide are added and the mixture is gradually heated to 200 ° C., at which temperature it is maintained for 0.75 hours. Then, 150 ml of hydrocarbon diluent is added and the mixture is filtered through diatomaceous earth and then distilled at 180 ° C. under a pressure of 2.63 kPa to obtain a product containing 1.46% of nitrogen, 2, 05% sulfur, 4.57% molybdenum (by

  neutron activation), 4.70% molybdenum (by fluorescent

  X-ray), 2.38% oxygen. Before the tests, this

  product is diluted with 100 g of neutral lubricating oil.

22.

EXAMPLE 18

  200 ml of hydrocarbon diluent, 50 ml of water and 33.5 g of ammonium paramolybdate are added to 292 g of the starting material described in Example 13. The mixture is refluxed for 21 hours and then distil to chase the water. After cooling to 140 ° C., 7 g of sulfur are added. The mixture is heated to 180-185 ° C and maintained at this temperature for 2 hours. After adding 100 ml of hydrocarbon diluent, the mixture is filtered through diatomaceous earth. 100 g of neutral oil are added as diluent and the mixture is distilled at 180 ° C. under a pressure of 2.63 kPa to obtain 414 g of product containing

  0.92% of nitrogen, 2.02% of sulfur, 4.57% of molybdenum

  neutron concentration), 4.60% molybdenum (fluorescence at

X-rays), 1.37% oxygen.

EXAMPLE 19

  200 ml of water and 116 g of MoO 3 are added in a

  3 liter capacity flask containing 1160 g of the succin-

  imide described in Example 1 and 800 ml of hydrogen diluent

  at 75 ° C. The mixture is refluxed for 3 hours and then distilled at 180 ° C. to drive off the water. At 110 ° C., about 64 g of H 2 S are added. Another 200 ml of hydrocarbon diluent is added and the mixture is filtered through diatomaceous earth and then distilled at 180 ° C. under a pressure of 2.63 kPa to obtain 1290 g of product containing 1.85% of nitrogen. , 24% sulfur, 5.92% molybdenum (neutron activation), 5.83% molybdenum (ray fluorescence)

X), 2.12% oxygen.

EXAMPLE 20

  200 ml of water and 116 g of MoO 3 are added to a 1-liter flask of capacity containing 1160 g of the succinimide described in Example 1 and 800 ml of hydrocarbon diluent at C. The mixture is stirred at reflux for 3 hours, then heated to 186 C to flush the water. After cooling to 1100C, 35 g of hydrogen sulfide are added. We heat the

  mixture at 182 ° C, then 200 ml of hydrogen diluent

  23. Carbonaceous and filtered on diatomaceous earth. Distillation at 180 ° C. under a pressure of 2.63 kPa gives 1272 g of product containing 1.93% of nitrogen, 3.20% of sulfur, 90% of molybdenum (neutron activation) and 3.01% of oxygen.

EXAMPLE 21

  50 ml of water and 29 g of MoO 3 are charged into a 1 liter flask containing 290 g of succinimide described in Example 1 and 200 ml of hydrocarbon diluent at 750 ° C. The mixture is stirred under reflux for 1 hour and then heated to 1870C to drive off the water. 100 ml of hydrocarbon diluent are then added and, at 75 ° C., 34 g of molybdenum polysulphide in aqueous solution (31% of free sulfur). This mixture is slowly heated to 1800C and maintained at this temperature for 2.25 hours. It is then filtered through diatomaceous earth and distilled at 1800 ° C. under a pressure of 2.63 kPa to obtain 318 g of product containing 1.89% of nitrogen, 4.07% of sulfur and 6.16% of sulfur.

  of molybdenum (neutron activation).

EXAMPLE 22

  50 ml of water and 29 g of MoO 3 are charged into a 1-liter flask containing 290 g of the succinimide described in Example 1 and 200 ml of hydrocarbon diluent at 750 ° C. This mixture is refluxed for 3 hours and then heated at 1950C to drive off the water. After cooling to 700 ° C., 58 g of a technical solution containing 52-60% of

  ammonium sulphide. The reaction mixture is heated to 180.degree.

  1850C for 4 hours. After cooling to 1150 ° C., 125 ml of hydrocarbon diluent is added, the mixture is filtered on diatomaceous earth and then distilled at 1800 ° C. under a pressure of 3.29 kPa to obtain 318 g of product.

  containing 6.19% molybdenum (X-ray fluorescence).

EXAMPLE 23

  50 ml of water and 22 g of MoO 3 are charged to a 1 liter flask containing 330 g of a concentrate, 24.

  containing 1.50% of nitrogen in the oil, a polyisobutenyl

  succinimide prepared from triethylenetetramine and a

  polyisobutenylsuccinic anhydride including the polyisobutenylsuccinic

  Butenyl has a molecular weight (number average) of 980, and 200 ml of hydrocarbon diluent at 75 ° C. This mixture is stirred at reflux (about 100 ° C.) for 11 hours. It is then heated to 180 C to flush the water. After cooling to C, 9 g of sulfur are added and the mixture is slowly heated to 180 ° C., at which temperature it is maintained for 3 hours. After addition of 100 ml of hydrocarbon diluent, the mixture is filtered through diatomaceous earth and then distilled at 180 ° C. under a pressure of 2.63 kPa to obtain 347 g of product containing 4.13% molybdenum (neutron activation). ) or 3.98% (X-ray fluorescence), 1.42% nitrogen, 2.66% sulfur and 2.85%

  of oxygen (neutron activation).

EXAMPLE 24

  50 ml of water and 29 g of MoO 3 are added to 291 g of the starting material used in Example 13 and 200 ml of hydrocarbon diluent at 75 ° C. The mixture is stirred at reflux for 3 hours and then heated. at 180 C to remove the water. After cooling to 140 ° C., 15 g of sulfur are added and the mixture is gradually heated to 180 ° -185 ° C., at which temperature it is maintained for 2.5 hours. After addition of 200 ml of hydrocarbon diluent, the mixture is filtered through diatomaceous earth and then 100 g of neutral oil is added as the diluent. By distillation under pressure at a pressure of 2.63 kPa, 410 g of product are obtained.

  containing 4.68% molybdenum (neutron activation).

EXAMPLE 25

  404 g of polyisobutenyl anhydride are charged with

  succinic acid having an index of polyisobutenyl anhydride

  76.7 in a 1 liter flask containing 47 g of tetraethylenepentamine. The mixture is heated to 150-160 ° C and maintained at this temperature for 1.5 hours. It is then distilled at 160 ° C. under 25 ° C.

  2.63 kPa pressure to obtain 439 g of polyisobutenyl-

  succinimide. 300 ml of hydrocarbon solvent, 135 ml of water and 80 g of MoO 3 are added to this succinimide. The mixture is stirred at reflux for 6 hours and then heated to 180 ° C to remove the water. After cooling to 140 ° C., 41 g of sulfur are added and the temperature is gradually raised to 180 ° -185 ° C., keeping it at this value for 4 hours. After the addition of 200 ml of diluent

  hydrocarbon, the mixture is filtered through diatomaceous earth

  Then, it was distilled at 2,000 ° C. under a pressure of 2.63 kPa and 300 g of neutral oil were added to give 810 g of product containing 6.23% molybdenum by X-ray fluorescence.

EXAMPLE 26

  50 ml of water and 29 g of MoO 3 are charged into a 1-liter flask containing 290 g of the succinimide described in Example 1 and 200 ml of hydrocarbon diluent with WC. The mixture is stirred at 96.degree.-900.degree. C. for 2 1/2 hours and then distilled at 191.degree. After cooling to 75 ° C., 43 ml of 1-butanethiol are added and the mixture is refluxed for 14 hours. The mixture is then distilled at 1800 ° C. under a pressure of 2.63 kPa to obtain 318 g of product containing 6.17% of molybdenum (X-ray fluorescence).

1.97% nitrogen and 1.05% sulfur.

EXAMPLE 27

  Lubricating oil compositions containing the additives prepared according to the invention have been tested in various tests. The results obtained in some of these tests, which are

described below.

  In the Oxidator B test, the stability of the oil is measured according to the time required to consume 1 liter of oxygen per 100 g of the test oil at 17 ° C. In the actual test, 25 g of oil are used and the results are returned to 100 g samples. The catalyst which is used in proportion of 1.38 cm3 by 26.

  cm3 of oil contains a mixture of soluble salts corre-

  95 ppm of copper, 80 ppm of iron, 4.8 ppm of manganese

  1100 ppm of lead and 49 ppm of tin. The results of

  this test shall be expressed in the hours necessary for the consumption

  1 liter of oxygen and for measuring the stability

to the oxidation of the oil.

  The anti-corrosion properties of compositions can be determined from their performance in the CRC L-38 bearing corrosion test. In this test, individual strips of copper and lead are immersed in the test lubricant and the test lubricant is heated for hours at a temperature of 146WC. The copper strip is weighed and then washed with a solution of potassium cyanide so as to remove the deposits of copper compounds. She is then weighed again. The weight losses of the two bands are reported as a measure of the degree of corrosion

under the effect of the oil.

  The copper tape test is a measure of corrosivity to non-ferrous metals and is described as ASTM D-130 test method. The anti-wear properties are measured by the four-ball wear test and the four-ball welding test. The four-ball wear test is described in ASTM D-2266 and is conducted at 54WC for 30 minutes using steel balls with a mass of 40 kg and the four-point weld test is a variation of the ASTM D-2783 test carried out at room temperature up to the point of welding with

  weight decreasing by 5 kg until the load of

  test was determined. The coefficient of friction

  a lubricating oil containing additives of the invention

  This was determined in the Kinetic Smooth Test Machine (KOTM) manufactured by G.M. Neely of Berkeley, California. The method used in this test is described by GL Neely in Proceeding of MidYear Meeting, American Petroleum Institute 1932, pages 60-74 and in ASLE Transactions, Volume 8, pages 1-11 (1965) and ASLE Transactions, Volume 7, pages 24. -31 (1964). The coefficient of friction was measured under the boundary conditions at 150 ° C. and 27 ° C. at 20 ° C. using a load of 1 kg and a ring filled with molybdenum resting on a cast iron disk. The results obtained in some of the essays on compositions

  of the invention are reproduced in the table below.

  Unless otherwise specified, the formulation under test contained in a lubricating oil

  neutral, 3.5% of a 50% polyisobutenyl succinimide concentrate, 20 mmol / kg of sulfurized calcium phenate, mmol / kg of

  magnesium sulfonate overbased, 5.5% viscosity index improver and 22 mmol / kg product of the invention. (If necessary, an additional quantity of succinimide is added to

  the total amount of nitrogen from the finished oil to 2.1%).

BOARD

  Example Oxidizer n B, h 1 1 9.6 13.1 11.8 11.0, 4 9.5 7.8 9.0 8.7 8.0 7, 8 7.9 7.4 9.0 ASTM

D-2266

  mm 0.42 0.43 0.49 0.52 0.37 0.43 0.51 0.55 0.53 0.46 0.40 0.48. ASTM

D-2783

  kg Cu, mg 21.2 21.9 18.3 19.9, 0 L-38 Pb, mg 0.5 1,0O, 3 1,2 0,4 D-130 Coefficient of friction oC 204 C 2a lb 2a 2a lb (1) (1) lb (1) lb (1) (1) (1) (1) lb / 2a (1) to (1) lb / 2a (1) lb (1) (2) 1a / lb (3) lb lc (1) 0.131 0.111 0.115 0.122 0.120 0.118 0.050 0.075 0.061 0.035 0.045 0, 100 0.081 0.060 0.040 0.039 No

  (1) molybdenum compound 4 proved 4% eo.ds in neutral oil.

  2 Conic of molybdenum at 6% by weight in neutral oil.

  Molybdenum compound proved to 5% by weight in the neutral oil.

PO J-. 1 ', 4, 29.

Claims (10)

  1. - Process for the production of a compound containing molybdenum, characterized in that it consists in combining an acidic molybdenum compound, a compound containing basic nitrogen, preferably a succinimide, a carboxylic acid amide, hydrocarbylpolyamine, Mannich base, phosphonamide, thiophosphonamide, phosphoramide or viscosity index improvers or mixtures thereof, and a sulfur source for   form a compound containing sulfur and molybdenum.   2. - Process according to claim 1, characterized in that the source of sulfur is sulfur, hydrogen sulfide, phosphorus pentasulfide, a compound of formula R2Sx, wherein R is a hydrocarbyl group and x is at least equal at 2, inorganic sulfides or inorganic polysulfides, thioacetamide, thiourea or mercaptans of formula RSH, wherein R is a hydrocarbyl group, or a sulfur-containing antioxidant, the sulfur source is preferably the sulfur, hydrogen sulfide, phosphorus pentasulfide, a compound of formula R2Sx wherein R is a C1 to C4 hydrocarbyl group and x is at least 3, an inorganic sulfide or an inorganic polysulfide, thioacetamide, thiourea, or a RSH compound in which R is a C1 to C40 alkyl group, and the acidic molybdenum compound is chosen from molybdic acid, ammonium molybdate and alkali metal molybdates, and in particular, the sourceSulfur is sulfur, hydrogen sulfide, RSH wherein R is C1-C10 alkyl, phosphorus pentasulfide or a compound of the formula (NH4) 2Sx, wherein x 'is at least equal to 1, the molybdenum acid compound is molybdic acid or ammonium molybdate and the basic nitrogen-containing compound is a succinimide, a carboxylic acid amide, a hydrocarbylpolyamine or a base of Mannich.   3. - A method according to claim 2, characterized in that the compound containing basic nitrogen is a C24 to C350 hydrocarbyl succinimide, a carboxylic acid amide 30. or a Mannich base prepared from an alkylphenol C9 to C200, formaldehyde and an amine. 4. Process according to claim 3, characterized in that the compound containing basic nitrogen is a polyisobutenyl succinimide prepared from   of polyisobutenyl succinic anhydride and tetra-   ethylenepentamine or triethylenepentamine, or the basic nitrogen compound is a carboxylic acid amide prepared from one or more carboxylic acids of formula R 2 COOH or a corresponding derivative which gives, by reaction with an amine, an amide of carboxylic acid, R2 being a C12-C3 alkyl or C12-C3 alkenyl group, and a hydrocarbylpolyamine, R2 being preferably C12-C20alkyl or C12-C20alkenyl and   the hydrocarbyl polyamine being preferably the tetra-   ethylenepentamine or triethylenetetramine.   5. - Process according to claim 2, characterized in that the compound containing basic nitrogen is a hydrocarbylpolyamine prepared from polyisobutenyl chloride and ethylenediamine,   ethylenetriamine, triethylenetetramine or tetra-   ethylenepentamine or mixtures thereof.   6. - Process according to claim 3, characterized in that the compound containing basic nitrogen is a Mannich base prepared from dodecylphenol, formaldehyde and methylamine or from a C80 to C100 alkylphenol, formaldehyde and triethylenetetramine or tetraethylenepentamine or their mixtures.   7. - Process according to any one of   Claims 1 to 6, characterized in that the reaction is   conduct in the presence of a polar activator which is preferably water.   8. - As a new industrial product, the product prepared by a process according to any one of Claims 1 to 7.   9. - Lubricating oil composition, 31. characterized in that it comprises an oil of viscosity suitable for lubrication and a proportion of 0.05 to 15% by weight.   product weight according to claim 8.   10. - Concentrated composition of lubricating oil, characterized in that it comprises an oil of viscosity suitable for lubrication and a proportion of 15 to   % by weight of product according to claim 8.