CA1174032A - Process of preparing molybdenum complexes, the complexes so produced and lubricants containing same - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Antioxidant additives for lubricating oil are prepared by combining an acidic molybdenum compound, a basic nitrogen compound complex, preferably in the presence of a polar promoter, and a sulfur source to form a sulfur- and molybdenum-containing composition.

Description

~174(~3~ -003 This invention relates to new lubricating oil composi-004 tions. ~ore specifically, it relates to new lubricating oil 005 compositions containing antioxidant molybdenum compounds.

007 Molybdenum disulfide has long been known as a 008 desirable additive for use in lubricating oil compositions.
009 However, one of its major detriments is its lack of oil 010 solubility. Molybdenum disulfide is ordinarily finely ground 011 and then dispersed in the lubricating oil composition to impart 012 friction modifying and antiwear properties. Finely ground 013 molybdenum disulfide is not an effective oxidation inhibitor in 014 lubricating oils.
015 As an alternative to finely grinding the molybdenum 016 disulfide, a number of different approaches involving preparing 017 salts of molybdenum compounds have been tried. One type of 018 compound which has been prepared is molybdenum dithiocar-019 bamates. Representative compositions are described in U.S.
020 patent 3,412,589, which teaches molybdenum (VI) dioxide dialkyl-021 dithiocarbamates; U.S. 3,509,051, which teaches sulfurized 022 oxymolybdenum dithiocarbamates; and U.S. 4,098,705, which 023 teaches sulfur containing molybdenum dihydrocarbyl dithio-024 carbamate compositions.
025 An alternative approach is to form dithiophosphates 026 instead of dithiocarbamates. Representative of this type of 027 molybdenum compound are the compositions described in U.S.
028 3,494,866, such as oxymolybdenum diisopropylphosphorodithioate.
029 U.S. 3,184,410 describes certain dithiomolybdenyl 030 acetylacetonates for use in lubricating oils.
031 Braithwaite and Greene in Wear, 46 (1978) 405-432 032 describe various molybdenum-containing compositions for use in 033 motor oils.
034 U.S. Patent 3,349,108 teaches a molybdenum trioxide 03S complex with diethylenetriamine for use as an additive for 036 molten steel.
037 Russian patent 533,625 teaches lube oil additives 038 prepared from ammonium molybdate and alkenylated polyamines.

1~7 ~32 Another way to incorporate molybdenum compounds in oil is to prepare a colloidal complex of molybdenum disulfide or oxysulfides dispersed using known dispersants. United States patent 3,223,625 describes a procedure 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 of the ether. United States 3,281,355 teaches the preparation of a dispersion of molybdenum disulfide by preparing a mixture of lubricating oil, dispersant, and a molybdenum compound in water or Cl_4 aliphatic alcohol, contacting this with a sulfide ion generator and then removing the solvent. Dispersants said to be effective in this procedure are petroleum sulfonates, phenates, alkylphenate sulfides, phosphosulfurized olefins and combinations thereof.
SUMMARY OF THE INVENTION
It has now been found that a lubricating oil additive can be prepared by combining an acidic molybdenum compound, a basic nitrogen-containing composition, preferably in the presence of a polar promoter, and a sulfur source to form a molybdenum and sulfur containing complex.
This invention provides a process for preparing a molybdenum-containing composition which comprises reacting an acidic molybdenum compound and a basic nitrogen compound selected from the group consisting of a succinimide, carboxylic acid amide, hydrocarbyl polyamines, Mannich base, phosphonamide, thiophosphoramide, phosphoramide, dispersant viscosity index improvers, or mixtures thereof, to form a molybdenum complex wherein from 0.01 to 2 atoms of molybdenum are present per basic nitrogen atom; and reacting said complex with a sulfur containing compound, in an amount to provide 0.1 to 4.0 atoms of sulfur per atom of molybdenum, to form a sulfur- and molybdenum-containing composition.

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DETAILED DESCRIPTION OF THE INVENTION
__ Lubricating oil compositions containing the additive prepared as disclosed herein are effective as either fluid and grease compositions (depending upon the specific additive or additives employed) for inhibiting oxidation, imparting anti-wear and extreme pressure properties, and/or modifying the friction properties of the oil which may, when used as a crank-case lubricant, lead to improved mileage.
The precise molecular formula of the molybdenum compositions of this invention is not known with certainty, however, they are believed to be compounds in which molybdenum, whose valences are satisfied with atoms of oxygen or sulfur, is either complexed by or the salt of one or more nitrogen atoms of the basic nitrogen containing composition used in the preparation of these compositions.
The molybdenum compounds used to prepare the compasi-tions of this invention are acidic molybdenum compounds.

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By acidic is meant that the molybdenum compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure. Typically these molybdenum compounds are hexavalent and are represented by the following compositions: molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkaline metal molybdates and other molybdenum salts such as hydrogen salts, e.g. hydrogen sodium molybdate, MoOC14, MoO2Br2, Mo203C16, molybdenum trioxide or similar acidic molybdenum compounds. Preferred acidic molybdenum compounds are molybdic acid, ammonium molybdate, and alkali metal molybdates. Particularly preferred are molybdic acid and ammonium molybdate.
The basic nitrogen compound must have a basic nitrogen content as measured by ASTM D-664 or D-2896. It is preferably oil-soluble. Typical of such compositions are succinimides, carboxylic acid amides, hydrocarbyl monoamines, hydrocarbon polyamines, Mannich bases, phosphonamides, thio-phosphoramides, phosphoramides, dispersant viscosity index improvers, and mixtures-thereof. These basic nitrogen-containing compounds are described below (keeping in mind the reservation that each must have at least one basic nitrogen). Any of the nitrogen-containing compositions may be after-treated with e.g, boron, using procedures well known in the art so long as the compositions continue to contain basic nitrogen. These after-treatments are particularly applicable to succinimides and Mannich base compositions.
The mono and polysuccinimides that can be used to prepare the lubricating oil additives described herein are disclosed in numerous references and are well known in the art. Certain fundamental types of succinimides and the related materials encompassed by the term of art "succinimide" are taught in United States patents 3,219,666, 3,172,892, and 3,272,746. The term "succinimide" is understood in the art to include many of the amide, imide, and amidine species which are also formed by this reaction. The predominant product however is a succinimide and this term has been generally accepted as meaning the product of a reaction of an 1~7~3Z

alkenyl substituted succinic acid or anhydride with a nitrogen containing compound. Preferred succinimides, because of their commercial availability, are those succinimides prepared from a hydrocarbyl succinic anhydride, wherein the hydrocarbyl group contains from about 24 to about 350 carbon atoms, and an ethylene amine, said ethylene amines being especially characterized by ethylene diamine, diethylene triamine, triethylene tetraamine, and tetraethylene pentamine. Particularly preferred are those succinimides prepared from polyisobutenyl succinic anhydride of 70 to 128 carbon atoms and tetraethylene pentaamine or triethylene tetraamine or mixtures thereof.
Also included within the term succinimide are the co-oligomers of a hydrocarbyl 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. Ordinarily this composition has between 1,500 and 50,000 average molecular weight. A typical compound would be that prepared by reacting polyisobutenyl succinic anhydride and ethylene dipiperazine.
Carboxylic amide compositions are also suitable starting materials for preparing the products of this invention. Typical of such compounds are those disclosed in United States patent 3,405,064. These compositions are ordinarily prepared by reacting a carboxylic acid or anhydride or ester thereof, having at least 12 to about 350 aliphatic carbon atoms in the principal aliphatic chain and, if desired, having sufficient pendant aliphatic groups to render the molecule oil soluble with an amine or a hydrocarbyl polyamine, such as an ethylene amine, to give a mono or polycarboxylic acid amide. Preferred are those amides prepared from (1) a carboxylic acid of the formula R2COOH, where R2 is C12 20 alkyl or a mixture of this acid with a polyisobutenyl carboxylic acid in which the polyisobut-enyl group contains from 72 to 128 carbon atoms and (2) an ethylene amine, especially triethylene tetraamine or tetraethylene pentaamine or mixtures thereof.

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~7~32 Another class of compounds which are useful in this invention are hydrocarbyl polyamines, preferably of the type disclosed in United States patent 3,574,576. The hydrocarbyl, which is preferably alkyl, or olefinic having one or two sites of unsaturation, usually contains from 9 to 350, preferably from 20 to 200 carbon atoms. Particularly preferred hydrocarbyl polyamines are those which are derived, e.g., by reacting poly-isobutenyl chloride and a polyalkylene polyamine, such as an ethylene amine, e.g. ethylene diamine, diethylene triamine, tetraethylene pentaamine, 2-aminoethylpiperazine, 1,3-propylene diamine, 1,2-propylenediamine and the like.
Another class of compounds useful for supplying basic nitrogen are the Mannich base compositions. These compositions are prepared from a phenol or C9 200 alkylphenol, an aldehyde, such as formaldehyde or formaldehyde precursor such as para-formaldehyde, and an amine compound. The amine may be a mono or polyamine and typical compositions are prepared from an alkyl-amine, such as methylamine or an ethylene amine, such as, diethylene triamine, or tetraethylene pentaamine and the like.
The phenolic material may be sulfurized and preferably is dodecylphenol or a C80 100 alkylphenol. Typical Mannich bases which can be used in this invention are disclosed in Canadian Patent 1,104,128 and United States Patents 4,157,309, 3,649,229, 3,368,972 and 3,539,663. The last application discloses Mannich bases prepared by reacting an alkylphenol having at least 50 carbon atoms, preferably 50 to 20G carbon atoms with formaldehyde and an alkylene polyamine HN(ANH)nH where A is a saturated divalent alkyl hydrocarbon of 2 to 6 carbon atoms and n is 1-10 and where the condensation product of said alkylene polyamine may be fur-ther reacted with urea or thiourea. The utility of these Mannich bases as starting materials for preparing lubricating oil ~ ~7~D32 additives can often be significantly improved by treating the Mannich base using conventional techniques to introduce boron into the composition.
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Another class of composition useful for preparing the additives of this invention are the phosphoramides and phosphonamides such as those disclosed in United States patents 3,909,430 and 3,968,157. These compositions may be prepared by forming a phosphorus compound having at least one P-N bond. They can be prepared, for example, by reacting phosphorus oxychloride with a hydrocarbyl diol in the presence of a monoamine or by reacting phosphorus oxychloride with a difunctional secondary amine and a mono-functional 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, l-hexene, 1,3-hexadiene, isobutylene, 4-methyl-1-pentene, and the like, with phosphorus pentasulfide and nitrogen-containing compound as defined above, particularly an alkylamine, alkyldiamine, alkylpo]yamine, or an alkyleneamine, such as ethylene diamine, diethylenetriamine, triethylene-tetraamine, tetraethylenepentaamine, and the like.
Another class of nitrogen-containing compositions useful in preparing the molybdenum compositions of this invention includes the so-called dispersant viscosity index improvers (VI improvers). These VI
improvers are commonly prepared by functionalizing a hydrocarbon polymer, especially a polymer derived from ethylene and/or propylene, optionally containing additional units derived from one or more co-monomers such as alicyclic or aliphatic olefins or diolefins. The functionalization may be carried out by a variety of processes which introduce a reactive site or sites which usually has at least one oxygen atom on the polymer. The polymer is then contacted with a nitrogen-containing source to introduce nitrogen-containing ~ ~74C~3Z

001 _7_ 002 functional groups on the polymer backbone. Commonly used 003 nitrogen sources include any basic nitrogen compound especially 004 those nitrogen-containing compounds and compositions described 005 herein. Preferred nitrogen sources are alkylene amines, such 006 as ethylene amines, alkyl amines, and ~annich bases.
007 Preferred basic nitrogen compounds for use in this 008 invention are succinimides, carboxylic acid amides, and Mannich 009 bases.
010 ~ Representative sulfur sources are sulfur, hydrogen 011 sulfide, sulfur monochloride, sulfur dichloride, phosphorus 012 pentasulfide, R2SX where R is hydrocarbyl, preferably Cl 40 013 alkyl, and x is at least 2, inorganic sulfides and polysulfides-014 such as (NH4)2SX, where x is at least 1, thioacetamide, thio-015 urea, and mercaptans of the formula RSH where R is as defined 016 above. Also useful as sulfurizing agents are traditional 017 sulfur-containing antioxidants such as wax sulfides and poly-018 sulfides, sulfurized olefins, sulfurized carboxylic and esters 019 and sulfurized ester-olefins, and sulfurized alkylphenols and 020 the metal salts thereof.
021 The sulfurized fatty acid esters are prepared by 022 reacting sulfur, sulfur monochloride, and/or sulfur dichloride 023 with an unsaturated fatty ester under elevated temperatures.
024 Typical esters include Cl-C20 alkyl esters of C8-C24 025 unsaturated fatty acids, such as palmitoleic, oleic, 026 ricinoleic, petroselinic, vaccenic, linoleic, linolenic, 027 oleostearic, licanic, paranaric, tariric, gadoleic, 028 arachidonic, cetoleic, etc. Particularly good results have 029 been obtained with mixed unsaturated fatty acid esters, such as 030 are obtained from animal fats and vegetable oils, such as tall 031 oil, linseed oil, olive oil, caster oil, peanut oil, rape oil, 032 fish oil, sperm oil, and so forth.
033 Exemplary fatty esters include lauryl tallate, methyl 034 oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl 035 linoleate, lauryl ricinoleate, oleyl linoleate, oleyl stearate, 036 and alkyl glycerides.
037 Cross-sulfurized ester olefins, such as a sulfurized 117~3Z

002 mixture of C10-C25 olefins with fatty acid esters of C10-C25 003 fatty afids and Cl-C25 alkyl or alkenyl alcohols, wherein the 004 fatty acid and/or the alcohol is unsaturated may also be used.
005 Sulfurized olefins are prepared by the reaction of 006 the C3-C6 olefin or a low-molecular-weight polyolefin derived 007 therefrom with a sulfur-containing compound such as sulfur, 008 sulfur monochloride, and/or sulfur dichloride.
009 Also useful are the aromatic and alkyl sulfides, such 010 as dibenzyl sulfide, dixylyl sulfide, dicetyl sulfide, 011 diparaffin wax sulfide and polysulfide, cracked wax-olefin 012 sulfides and so forth. They can be prepared by treatin~ the 013 starting material, e.g., olefinically unsaturated compounds, 014 with sulfur, sulfur monochloride, and sulfur dichloride.
015 Particularly preferred are the paraffin wax thiomers described 016 in U.S. Pat. No. 2,346,156.
017 Sulfurized alkyl phenols and the metal salts thereof 018 include compositions such as sulfurized dodecylphenol and the 019 calcium salts thereof. The alkyl group ordinarily contains 020 from 9-300 carbon atoms. The metal salt may be preferably, a 021 group I or group II salt, especially sodium, calcium, 022 magnesium, or barium.
023 Preferred sulfur sources are sulfur, hydrogen 024 sulfide, phosphorus pentasulfide, R2SX where R is hydrocarbyl, 025 preferably Cl 10 alkyl, and x is at least 3, mercaptans wherein 026 R is Cl 10 alkyl, inorganic sulfides and polysulfides, 027 thioacetamide, and thiourea. Most preferred sulfur sources are 028 sulfur, hydrogen sulfide, phosphorus pentasulfide, and 029 inorganic sulfides and polysulfides.
030 The polar promoter which is preferably used in the 031 process of this invention is one which facilitates the inter-032 action between the acidic molybdenum compound and the basic 033 nitrogen compound. A wide variety of such promoters are well 034 known to those skilled in the art. Typical promoters are 1,3-035 propanediol, 1,4-butanediol, diethylene glycol, butyl cello-036 solve, propylene glycol, 1,4-butyleneglycol, methyl carbitol, 037 ethanolamine, diethanolamine, N-methyl-diethanol-amine, 1~'74(D3;~

002 dimethyl formamide, N-methyl acetamide, dimethyl acetamide, 003 methanol, ethylene glycol, dimethyl sulfoxide, hexamethyl 004 phosphoramide, tetrahydrofuran and water. Preferred are water 005 and ethylene glycol. Particularly preferred is water.
006 While ordinarily the polar promoter is separately 007 added to the reaction mixture, it may also be present, par-008 ticularly in the case of water, as a component of non-anhydrous 009 starting materials or as waters of hydration in the acidic 010 molybdenum compound, such as (NH4)6Mo7O24.4 H2O. Water may 011 also be added as ammonium hydroxide.
012 A method for preparing compositions of this invention 013 is to prepare a solution of the acidic molybdenum precursor and 014 a basic nitrogen-containing compound preferably in the presence 015 of a polar promoter with or without diluent. The diluent is 016 used, if necessary, to provide a suitable viscosity for easy 017 stirring. Typical diluents are lubricating oil and liquid 018 compounds containing only carbon and hydrogen. If desired, 019 ammonium hydroxide may also be added to the reaction mixture to 020 provide a solution of ammonium molybdate. This reaction is 021 carried out at a temperature from the melting point of the 022 mixture to reflux temperature. It is ordinarily carried out at 023 atmospheric pressure although higher or lower pressures may be 024 used if desired. This reaction mixture is treated with a 025 sulfur source as defined above at a suitable pressure and 026 temperature for the sulfur source to react with the acidic 027 molybdenum and basic nitrogen compounds. In some cases, 028 removal of water from the reaction mixture may be desirable 029 prior to completion of reaction with the sulfur source.
030 In the reaction mixture, the ratio of molybdenum 031 compound to basic nitrogen compound is not critical; however, 032 as the amount of molybdenum with respect to basic nitrogen 033 increases, the filtration of the product becomes more diffi-034 cult. Since the molybdenum component probably oligomerizes, it 035 is advantageous to add as much molybdenum as can easily be 036 maintained in the composition. Usually, the reaction mixture 037 will have charged to it from 0.01 to 2.00 atoms of molybdenum ~ ~74~3~

002 per basic nitrogen atom. Preferably from 0.4 to 1.0, and most 003 preferably from 0.4 to 0.7, atoms of molybdenum per atom of 004 basic nitrogen is added to the reaction mixture.
005 The sulfur source is usually charged to the reaction 006 mixture in such a ratio to provide 0.1 to 4.0 atoms of sulur 007 per atom of molybdenum. Preferably from 0.5 to 3.0 atoms of 008 sulfur per atom of molybdenum is added, and most preferably, 009 1.0 to 2.6 atoms of sulfur per atom of molybdenum.
010 The polar promoter, which is optionally and prefer-011 ably used, is ordinarily present in the ratio of 0.1 to 50 mols 012 of promoter per mol of molybdenum. Preferably from 0.5 to 25 013 and most preferably 1.0 to 15 mols of the promoter is present 014 per mol of molybdenum.
015 The lubricating oil compositions containing the 016 additives of this invention can be prepared by admixing, by 017 conventional techniques, the appropriate amount of the molyb-018 denum-containing composition with a lubricating oil. The 019 selection of the particular base oil depends on the contem-020 plated application of the lubricant and the presence of other 021 additives. Generally, the amount of the molybdenum containing 022 additive will vary from 0.05 to 15% by weight and preferably 023 from 0.2 to 10~ by weight.
024 The lubricating oil which may be used in this 025 invention includes a wide variety of hydrocarbon oils, such as 026 naphthenic bases, paraffin bases and mixed base oils as well as 027 synthetic oils such as esters and the like. The lubricating 028 oils may be used individually or in combination and generally 029 have a viscosity which ranges from 50 to 5,000 SUS and usually 030 from 100 to 15,000 SUS at 38C.
031 In many instances it may be advantageous to form 032 concentrates of the molybdenum containing additive within a 033 carrier liquid. These concentrates provide a convenient method 034 of handling and transporting the additives before their subse-035 quent dilution and use. The concentration of the molybdenum-036 containing additive within the concentrate may vary from 0.25 037 to 90% by weight although it is preferred to maintain a con-~1~4~32 002 centration between 1 and 50% by weight. The final application 003 of the lubricating oil compositions of this invention may be in 004 marine cylinder lubricants as in crosshead diesel engines, 005 crankcase lubricants as in automobiles and railroads, lubri-006 cants for heavy machinery such as steel mills and the like, or 007 as greases for bearings and the like. Whether the lubricant is 008 fluid or a solid will ordinarily depend on whether a thickening 009 agent is present. Typical thickening agents include polyurea 010 acetates, lithium stearate and the like.
011 If desired, other additives may be included in the 012 lubricating oil compositions of this invention. These addi-013 tives include antioxidants or oxidation inhibitors, disper-014 sants, rust inhibitors, anticorrosion agents and so forth.
015 Also anti-foam agents stabilizers, anti-stain agents, tackiness 016 agents, anti-chatter agents, dropping point improvers, anti-017 squawk agents, extreme pressure agents, odor control agents and 018 the like may be included.
019 Certain molybdenum products that can be prepared by 020 the process of invention also find utility in making brake 021 lining materials, in high-temperature structural materials, in 022 iron and steel alloys, in cladding materials, in electroplating 023 solutions, as components for electrical discharge machine 024 electrodes, as fuel additives, in making self-lubricating or 025 wear-resistant structures, as mold release agents, in composi-026 tions for phosphatizing steel, in brazing fluxes, in nutrient 027 media for microorganisms, in making electrosensitive recording 028 material, in catalysts for refining coal, oil, shale, tar 029 sands, and the like or as stabilizers or curing agents for 030 natural rubber or polymers.
031 The following examples are presented to illustrate 032 the operation of the invention and are not intended to be a 033 limitation upon the scope of the claims.
034 Example 1 035 To a 500 ml flask was added 290 grams of a solution 036 of 45% concentrate in oil of the succinimide prepared from 037 polyisobutenyl succinic anhydride and tetraethylene pentaamine 1~7~p3~

002 and having a number average molecular weight for the 003 polyisobutenyl group of about 980 and 150 ml hydrocarbon 004 thinner. The mixture was heated to 120C. Then over a period 005 of 45 minutes at 100 to 110C, there was added a solution 006 containing 28.8 grams molybdenum trioxide dissolved from 12.9 007 grams of concentrated ammonium hydroxide diluted to 100 ml with 008 water (0.21 mols of ammonia). ~he reaction mixture was heated 009 to refluxing (approximately 155C) and held at this temperature 010 for one hour. Hydrogen sulfide gas was added at 115C. A
011 total of 10 grams hydrogen sulfide was added and then the 012 reaction mixture was flushed with nitrogen for one hour at 013 110C. The mixture was then heated to 155C and held at this 014 temperature for one hour. To the mixture was added 100 ml of 015 hydrocarbon thinner and then the mixture was filtered hot 016 through diatomaceous earth. The product was stripped to 160C
017 at 20 mm Hg to yield 316.6 grams of product containing 4.94%
018 molybdenum, 2.77~ oxygen, 2.10% sulfur and 1.91% nitrogen.
019 Example 2 020 A solution of 28.8 grams molybdenum trioxide 021 dissolved in 0.2 mols ammonia from 12.9 ml of concentrated 022 ammonium hydroxide diluted to 100 ml with water was added 023 dropwise over a period of 45 minutes at 100 to 105C to a 024 solution of 290 grams of the succinimide described in Example 025 1. The reaction mixture was heated to reflux at approximately 026 155C and held at this temperature for one hour. The mixture 027 was then heated to 140C and 4 grams sulfur was added. The 028 temperature was increased to reflux at 155C and held at reflux 029 for one hour. The temperature was then increased to 165 to 030 170C and held for two hours. To the mixture was then added 031 100 ml of hot hydrocarbon thinner to give approximately 200 ml 032 of solvent in the reaction flask. The mixture was filtered hot 033 through diatomaceous earth and then stripped at 160C and 20 mm 034 Hg to give 312.8 grams of product containing 5.39~ molybdenum, 035 1.75% nitrogen, 3.50% oxygen and 1.30% sulfur.
036 Example 3 037 To a 1 liter flask was added 290 grams of the ~ :~L74~3Z
succinimide described in Example 1 and 150 ml hydrocarbon thinner. The reaction mixture was heated to 65C and 28.8 grams of molybdenum trioxide and 50 ml of water was added. The temperature was maintained at 65 to 70C for 1/2 hour and then raised to 150C. After 50 minutes and at 150 C, 5 grams of elemental sulfur and 50 ml of hydrocarbon thinner was added. The temperature was increased to 155 to 160C (reflux) over a period of 1/2 hour. Some solvent was removed and the temperature was increased to 165 to 170C. The mixture was held at this temperature for two hours. To the mixture was added 50 ml of hydrocarbon thinner and the mixture was filtered through diatomaceous earth and then stripped to 160C at 20 mm Hg to yield 314.5 grams of product containing 4.93% molybdenum, 3.59, 3.48% oxygen, 1.92% nitrogen and 1.49% sulfur.
Example 4 To a 1 liter flask was added 290 grams of the succinimide described in Example 1 and 150 ml hydrocarbon thinner. The mixture was heated to 65C and 28.8 grams molybdenum trioxide, and 50 ml water was added. The temperature was maintained at 65C for 1/2 hour and increased to 150C over a period of 55 minutes. To the mixture was added 7 grams elemental sulfur and 100 ml of hydrocarbon thinner. The reaction mixture was maintained at reflux at approximately 155C for 45 minutes and then the temperature was increased to 165 to 170C and held there for two hours. To the mixture was added 50 ml of hydrocarbon thinner and the reaction mixture was filtered hot through diatomaceous earth. The filtrate was stripped to 160C at 20 mm Hg to yield 316.5 grams of product containing 6.35% molybdenum, 3.57% oxygen, 1.86% nitrogen, 2.15% sulfur.
Example 5 To a 1 liter flask was added 290 grams of the succinimide described in Example 1, 28.2 grams molybdenum trioxide, 50 ml water and 150 ml hydrocarbon thinner. The reaction mixture was heated to 65 C and maintained at this temperature for 1/2 hour. Then 6 grams of hydrogen sulfide was added at 63-65 C over a period of 15 minutes. ~fter addition, the temperature was -13-i~ ,.,~

4~32 002 maintained at 53-65C for one hour with vigorous stirring and 003 under nitrogen atmosphere. The temperature was then raised to 004 100C to remove most of the water and then to 155 to 160C and 005 held at reflux for one hour. The mixture was filtered hot 006 through diatomaceous earth and then stripped to 160C at 20 mm 007 Hg to yield 314.15 grams of product containing 5.87% molyb-008 denum, 3.64~ oxygen, 2.05% nitrogen, 0.75% sulfur and 0.08%
009 sediment.
010 Example 6 011 To a l-liter flask was added 290 grams of the 012 succinimide described in Example 1 and 150 ml hydrocarbon 013 thinner. The reaction mixture was heated to 65C and 28.8 014 grams molybdenum trioxide and 50 ml of water was added. The 015 temperature was held at 65C for 1j2 hour and raised slowly to 016 155C at 120C, 10 grams of elemental sulfur was added and the 017 reaction mixture was then held at 155C for 30 minutes, 160C
018 for 15 minutes, 170C for 30 minutes, 175C for 30 minutes and 019 180C for 30 minutes. Then 120 ml of hydrocarbon thinner was 020 added and the reaction mixture was filtered through diatoma-021 ceous earth and the filtrate stripped to 160C at 20 mm Hg to 022 yield a product containing 5.70% molybdenum, 2.88% oxygen, 023 1.83% nitrogen, and 2.94% sulfur.
024 Example 7 025 To a 3-liter flask was added 1160 grams of 026 succinimide described in Example 1 and 800 ml of hydrocarbon 027 thinner. The reaction mixture was heated to 65C and 200 ml 028 water and 116 grams ~oO3 was added. The temperature was 029 increased to reflux (98C) and held at this temperature for 030 2-1/2 hours until the solution became clear green. Water was 031 removed at up to a temperature of 140C (bottoms). Then 60 032 grams of sulfur was added. The temperature was increased to 033 155C over a period of 15 minutes and held at this temperature 034 for 1/2 hour. The temperature was then increased to 180C over 035 a period of 30 minutes and held at this temperature for 3-1/2 036 hours. The mixture was then cooled and left overnight. Then 037 200 ml hydrocarbon thinner solvent was added and the solution ~74~D32 heated to 130C. It was then filtered through diatomaceous earth and stripped to 200C at 20 mm Hg to yield 1287 grams of product containing 4.49% sulfur, 5.82% molybdenum and 2.58% oxygen.
Example 8 To a 3-liter flask was added 1160 grams of a polyamide prepared from a C18 carboxylic acid and tetraethylene pentaamine and containing 6.29% nitrogen and 800 ml hydrocarbon thinner. The mixture was heated to 65C and 200 ml of water and 116 grams MoO3 was added. The temperature was raised to reflux, approximately 95C, and held at this temperature for 4 ]0 hours until the solution became clear green. The solvent was removed to 150 C maximum and the mixture was then cooled to 140C and 28 grams sulfur was added. The temperature was raised to 155C over a period of 1/4 hour and held at this temperature for 1/2 hour. The temperature was again increased to 175C over a period of 20 minutes and then held at between 175 and 180C for 2 hours. The mixture was cooled and left overnight and then 200 ml hydrocarbon solvent was added. The mixture was heated to 130C, filtered through diatomaceous earth and then stripped to 180C bottoms at 20 mm Hg to yield 1282 grams of product containing 5.45% nitrogen, 2.15%
sulfur, 5.51% molybden~m, and 5.73% oxygen.
Example 9 To a l-liter flask was added 400 grams of the reaction product of polyisobutenylchloride wherein the polyisobutene group has a number average molecular weight of 1,400 and ethylene diamine in a hydrocarbon solvent. The mixture was stripped to 160C bottoms at 20 mm Hg and cooled to yield 289 grams of product containing 1.58% nitrogen. To this was added 200 ml of hydrocarbon thinner, 50 ml water and 29 grams of MoO3. The mixture was stirred at reflux, approximately 101C for 2 hours, and then stripped to 140C bottoms. Then 7 grams of sulfur was added and the temperature was increased to 155 C over a period of 10 minutes and held 30 at this temperature for 1/2 hour. The temperature was then raised to 180 C
over a ~i7~L~3Z

002 period of 10 minutes and held at 180 to 185C for 2 hours.
003 The mixture was cooled and 100 ml hydrocarbon thinner was 004 added. The mixture was then filtered through diatomaceous 005 earth and after an addition of 100 grams of neutral lubricating 006 oil was stripped to 180C bottoms at 20 mm Hg to yield 40 007 grams of product.
008 Example 10 009 To a l-liter flask was added 290 grams of a Mannich 010 base prepared from dodecylphenol, methylamine and formaldehyde 011 and having an alkalinity value of 110 and containing 2.7%
012 nitrogen, and 200 ml of a hydrocarbon thinner. The mixture was 013 heated to 65C and 50 ml water and 29 grams of molybdenum tri-014 oxide was added. The mixture was stirred at reflux, 104 to 015 110C, for 4-1/2 hours. The solution became a clear dark brown 016 color and then was stripped to 175C bottoms. The mixture was 017 cooled to 140C and 7 grams sulfur was added. The temperature 018 was increased to 155C over a period of 7 minutes and held at 019 this temperature for 1/2 hour. The temperature was then 020 increased to 180C over a period of 10 minutes and held for 2 021 hours. The mixture was then cooled and left overnight. The 022 next day 100 ml of hydrocarbon solvent was added. The mixture 023 was heated to loOC and filtered through diatomaceous earth and 024 then strippec to 180C at 20 mm Hg to yield 317 grams of 025 product.
026 Example 11 027 To a 3-liter flask was added 1160 grams of succini-028 mide as described in Example 1 and 800 ml of hydrocarbon 029 thinner. This mixture was heated tO 65C and 200 ml water and 030 116 grams of MoO3 was added. The mixture was stirred at reflux 031 (96C) for 2 hours. It was cooled and an additional 116 grams 032 of MoO3 was added. This mixture was stirred at reflux (97C) 033 for 10 hours. The mixture was cooled and allowed to stand over-034 night. It was then stripped to 180C, cooled to 140 and 60 035 grams of sulfur was added. The temperature was then increased 036 to 155C over a period of 15 minutes and held at this tempera-037 ture for 1/2 hour and then heated to 180C over a period of 15 1~7 ~Q32 002 minute and held at this temperature for 3 hours. The mixture 003 was cooled and 200 ml hydrocarbon thinner was added. Then the 004 solution was heated to 130C and filtered through diatomaceous 005 earth with addition of hydrocarbon thinner to aid in-filtra-006 tion. The filtrate was stripped to 200C and 20 mm Hg to yield 007 1325 grams of product.
008 Example 12 (B-3721-49) 009 To a 1 liter flask was added 400g of the hydrocarbyl 010 polyamine described in Example 9 which was stripped to 160C at 011 20 mm Hg and then 200 ml hydrocarbon thinner, 50 ml water and 012 29g MoO3 was added. The mixture was stirred at 101C for 2 013 hours and then heated to 140C to remove water. Sulfur (7g) 014 was added and the temperature was gradually increased to 015 180-185C where it was held for 2 hours. After cooling, 100 ml 016 hydrocarbon thinner was added a,nd the mixture was filtered 017 through diatomaceous earth and stripped at 180C and 20 mm Hg 018 to yield 409g of product containing Mo 4.67% (neutron 019 activation), 4.93 (x-ray fluorescense); O, 1.37%; S, 1.94%.
020 Example 13 021 To a 1 liter flask containing at 65C 289g of the 022 stripped polyamine described in Example 12 and 200 ml 023 hydrocarbon thinner was added 50 ml water and 29g MoO3. The 024 mixture was stirred at reflux for 2 hours and then stripped at 025 175C. After cooling to 110-115C, lOg of H2S was added. Then 026 the mixture was heated to 155-160C and held for 1 hour. After 027 cooling, 75 ml hydrocarbon thinner was added and the mixture 028 was filtered through diatomaceous earth. Neutral oil (lOOg) 029 was added and the mixture was stripped to 180C at 20 mm Hg to 030 yield 412g of product containing N, 0.90~; S, 2.31%; Mo, 4.21 031 (N.A.), 4.67 (XRF); O, 1.01.
032 Example 14 033 To'a 1 liter flask containing 300g of a borated Mannich 034 base prepared from a C80 100 alkylphenol, formaldehyde and 035 tetraethylene pentaamine or triethylene tetraamine, or mixtures 036 thereof and containing urea (Amoco 9250) and 200 ml hydrocarbon 037 thinner at 65C was added 40 ml water and 25g MoO3. The ~1741~32 002 mixture was stirred at reflux for 4.5 hours and then stripped 003 to 165C. After cooling to 140C, 7g sulfur was added and the 004 temperature was gradually increased to 185C where it was held 005 for 2 hours. Then, 75 ml hydrocarbon thinner was added and the 006 mixture was filtered through diatomaceous earth and then 007 stripped to 180C at 20 mm Hg to yield 307g product containing 008 N, 1.04%; S, 2.53~; Mo, 4.68% (N.A.), 4.99% (XRF); O, 2.53%; B, 009 0.22%.
010 Example 15 011 To a 3 liter flask was added 5009 of a concentrate of 012 polyisobutenyl succinic anhydride wherein the polyisobutenyl 013 group had a number average molecular weight of about 980 and 014 369 dimethyl aminopropylamine. The temperature of the reaction 015 mixture was increased to 160C, held there for 1 hour and then 016 stripped to 170C at 20 mm Hg. To this mixture was added 350 017 ml hydrocarbon thinner, 50 ml water, and 29g MoO3. This 018 mixture was stirred at reflux for 2 hours and then stripped to 019 140C to remove water. Then 79 of sulfur was added and the 020 mixture was held at 180-185C for 2 hours. After cooling, 021 additional hydrocarbon thinner was added and the mixture was 022 filtered through diatomaceous earth, and then stripped to 180C
023 at 20 mm Hg to yield 336g product containing N, 1.17%; S, 024 1.55~; Mo, 3.37% (N.A.), 3.31% (XRF); O, 2.53%.
025 Example 16 026 To a 1 liter flask containing 2909 of the succinimide 027 described in Example 1 and 200 ml of hydrocarbon thinner at 028 65C was added 50 ml water and 2Sg MoO3. The mixture was 029 stirred at reflux for 1.5 hours and then stripped to 165C to 030 remove water. After cooling to 100C, 409 butyldisulfide was 031 added and the mixture was heated to 180-185C for 2.5 hours.
032 Then an additional 100 ml hydrocarbon thinner was added before 033 filtering through diatomaceous earth and stripping to 180C at 034 20 mm Hg to yield 305g of product containing N, 1.90%; S, 0.47%;
035 Mo, 6.21% (N.A.), 6.34% (XRF), O, 4.19 (N.A.).
036 Example 17 037 To a 1 liter flask containing 290g of the succinimide 1~7~3Z

002 described in Example 1 and 200 ml hydrocarbon thinner at 75C
003 was added 50 ml water and 29g MoO3. The mixture was refluxed 004 for 1.5 hours and then stripped to 200C to remove water.
005 After cooling to 100C, l9g thioacetamide was added and the 006 mixture was gradually heated to 200C where it was held for 007 0.75 hours. Thenr 150 ml hydrocarbon thinner was added and the 008 mixture was filtered through diatomaceous earth and stripped to 009 180C at 20 mm Hg, to yield a product containing N, 1.46%; S, 010 2.05%; Mo, 4.57% (N.A.), 4.70~ (XRE); O, 2.38%. Before 011 testing, this product was diluted with lOOg neutral lubricating 012 oil.
013 Example 18 014 To 292g of the starting material described in Example OlS 13 was added 200 ml hydrocarbon thinner, 50 ml water, and 33.5g 016 ammonium paramolybdate. The mixture was refluxed for 21 hours 017 and then stripped to remove water. After cooling to 140C, 7g 018 sulfur was added. The mixture was heated to 180-185C and held 019 for 2 hours. After addition of 100 ml hydrocarbon thinner, the 020 mixture was filtered through diatomaceous earth. Neutral 021 diluent oil (lOOg) was added and the mixture was stripped to 022 180C at 20 mm Hg to yield 414g product containing N, 0.92%; S, 023 2.02%; Mo, 4.57% (N.A.), 4.60% (XRF); O, 1.37%.
024 Example 19 025 To a 3 liter flask containing 1160g of the succini-026 mide described in Example 1 and 800 ml hydrocarbon thinner at 027 75C was added 200 ml water and 116g MoO3. The mixture was 028 refluxed for 3 hours and then stripped to 180C to remove 029 water. At 110C, about 64g H2S was added. Additional hydro-030 carbon thinner (200 ml) was added and the mixture was filtered 031 through diatomaceous earth and then stripped to 180C at 20 mm 032 Hg to yield 1290g of product containing N, 1.85~; S, 4.24%; Mo, 033 5.92 (N.A.), 5.83% (XRF), O, 2.12%.
034 Example 20 035 To a 1 liter flas~ containing 1160g of the succini-036 mide described in Example 1 and 800 ml hydrocarbon thinner at 037 75C was added 200 ml water and 116g ~oO3. The mixture was ~.~74~32 002 stirred at reflux for 3 hours and then heated to 186C to 003 remove water. After cooling to 110C, 35g H2S was added. The 004 mixture was heated to 182C, then 200 ml hydrocarbon thinner 005 was added and the mixture was filtered through diatomaceous 006 earth. Stripping to 180C at 20 mm Hg yielded 1272g of product 007 containing N, 1.93%; S, 3.20%; Mo, 5.90~ (N.A.); O, 3.01%.
008 Example 21 009 To a 1 liter flask containing 290g of the succinimide 010 described in Example 1 and 200 ml hydrocarbon thinner at 75C
011 was added 50 ml water and 29g MoO3. The mixture was stirred at 012 reflux for 1.5 hours and then heated to 187C to remove water.
013 Then 100 ml hydrocarbon thinner was added and, at 75C, 34g of 014 aqueous ammonium polysulfide (31% free sulfur). This mixture 015 was slowly heated to 180C and held there for 2.25 hours. It 016 was then filtered through diatomaceous earth and stripped to 017 180C at 20 mm Hg to yield 318g of product containing N, 1.89%;
018 S, 4.07%; Mo, 6.16% (N.A.).
019 Exam~le 22 020 To a 1 liter flask containing 290g of the succinimide 021 described in Example 1 and 200 ml hydrocarbon thinner at 75C
022 was added 50 ml water and 29g MoO3. This mixture was refluxed 023 for 3 hours and then heated to 195C to remove water. After 024 cooling to 70C, 58g of a 52-60% technical solution of ammonium 025 sulfide was added. The reaction mixture was heated to 026 180-185C for 4 hours. After cooling to 115C, 125 ml hydro-027 carbon thinner was added, the mixture was filtered through 028 diatomaceous earth, and then stripped to 180C at 25 mm Hg to 029 yield 318g of product containing 6.19~ Mo (XRF).
030 Example 23 031 To a 1 liter flask containing 330g of a concentrate 032 containing l.S0~ ~ in oil of a polyisobutenyl succinimide 033 prepared from triethylenetetraamine and a polyisobutenyl 034 succinic anhydride wherein the polyisobutenyl group has a 035 number average molecular weight of 980, and 200 ml hydrocarbon 036 thinner at 75C was added 50 ml water and 22g MoO3. This 037 mixture was stirred at reflux (about 100C) for 11 hours. It 1:~74C~

002 was then heated to 180C to remove water. After cooling to 003 140C, 99 sulfur was added and the mixture was slowly heated to 004 180C where it was held for 3 hours. After adding 100 ml 005 hydrocarbon thinner, the mixture was filtered through diato-006 maceous earth and then stripped to 180C at 20 mm Hg to yield 007 347g of product containing Mo, 4.13% (N.A.), 3.98% (XRF); ~, 008 1.42%; S, 2.66%; O, 2.85% (N.A.).
009 Example 2_ 010 To 291g of the starting material used in Example 13 011 and 200 ml hydrocarbon thinner at 75C was added 50 ml water 012 and 29g MoO3. The mixture was stirred at reflux for 3 hours 013 and then heated to 180C to remove water. After cooling to 014 140C, 15g of sulfur was added and the mixture was gradually 015 heated to 180-185C where it was held for 2.5 hours. After 016 adding 200 ml hydrocarbon thinner, the mixture was filtered 017 through diatomaceous earth and then lOOg neutral diluent oil 018 was added. Stripping to 200C at 20 mm Hg yielded 4109 of 019 product containing Mo, 4.68% (N.A.).
020 Example 25 021 To a 1 liter flask containing 47g tetraethylene 022 pentaamine was added 404g polyisobutenyl succinic anhydride 023 having a PI~SA number of 76.7. The mixture was heated to 024 150-160C where it was held for 1.5 hours. It was then 025 stripped to 160C at 20 mm Hg to yield 4399 of polyisobutenyl 026 succinimide. To this succinimide was added 300 ml hydrocarbon 027 solvent, 135 ml water, and 80g MoO3. The mixture was stirred 028 at reflux for 6.5 hours and then heated to 180C to remove 029 water. After cooling to 140C, 41g sulfur was added and the 030 temperature gradually increased to 180-185C where it was held 031 for 4 hours. After addition of 200 ml hydrocarbon thinner, the 032 mixture was filtered through diatomaceous earth and then 033 stripped to 200C at 20 mm ~9 and 300g neutral oil was added to 034 yield 810g of product containing 6.23% Mo by XRF.
035 Example 26 036 To a 1 liter flask containing 290g of the succinimide 037 described in Example 1 and 200 ml hydrocarbon thinner at 75C

~7~32 002 was added 50 ml water and 29g Mo03. The mixture was stirred at 003 95-98C for 2-1/2 hours and then stripped at 191C. After 004 cooling to 75C, 43 ml l-butanethiol was added and the mixture 005 was refluxed for 14 hours. The ~ixture was then stripped to 006 180C at 20 mm Hg to yield 318g product containing Mo, 6.17 007 (XRF); N, 1.97%; S, 1.05~.
008 Example 27 009 Lubricating oil compositions containing the additives 010 prepared according to this invention have been tested in a 011 variety of tests. Reported below are results from certain of 012 these tests which are described as follows.
013 In the Oxidator B test the stability of the oil is 014 measured by the time required for the consumption of 1 liter of 015 oxygen by 100 grams of the test oil at 340F. In the actual 016 test/ 25 grams of oil is used and the results are~corrected to 017 100-gram samples. The catalyst which is used at a rate of 1.38 018 cc per 100 cc oil contains a mixture of soluble salts providing 019 95 ppm copper, 80 ppm iron, 4.8 ppm manganese, 1100 ppm lead, 020 and 49 ppm tin. The results of this test are reported as hours 021 to consumption of 1 liter of oxygen and our measure of the oxi-022 dative stability of the oil.
023 The anti-corrosion properties of compositions can be 024 tested by their performance in the CRC L-38 bearing corrosion 025 test. In this test, separate strips of copper and lead are 026 immersed in the test lubricant and the lubricant is heated for 027 20 hours at a temperature of 295F. The copper strip is 028 weighed and then washed with potassium cyanide solution to 029 remove copper compcund deposits. It is then re-weighed. The 030 weight losses of the two strips are reported as a measure of 031 the degree of corrosion caused by the oil.
032 The copper strip test is a measure of corrosivity 033 toward non-ferrous metals and is described as ASTM Test Method 034 D-130. Anti-wear properties are measured by the 4-ball wear 035 and the 4-ball weld tests. The 4-ball wear test is described 036 in ASTM D-2266 and is run at 54C for 30 minutes using steel 037 balls and a 40 kg weight and the 4-ball weld test is a ~7~C~3Z

002 variation of ASTM D-2783 run at ambient temperature until weld 003 point with weights decreased by 5 kg until the pass load is 004 determined. The coefficient of friction of a lubricating oils 005 containing additives of this invention was tested in the 006 Kinetic Oiliness Testing Machine (KOTM) manufactured by G. M.
007 Neely of Berkeley, California. The procedure used in this test 008 is described by G. L. Neely, Proceeding of Mid-Year Meeting, 009 American Petroleum Institute 1932, pages 60-74 and in ASLE
010 Transactions, Vol. 8, pages 1-11 (1965) and ASLE Transactions, 011 Vol. 7, pages 24-31 (1964). The coefficient of friction was 012 measured under boundary conditions at 150 and 204C using a 1 013 Kg load and a molybdenum-filled ring on a cast-iron disk. The 014 dàta for some of the tests run on compositions of this 015 invention is reported in the Table below.
016 Unless otherwise noted, the formulation tested 017 contained, in a neutral lubricating oil, 3.5% of a 50~ concen-018 trate of polyisobutenyl succinimide 20 mmoles/kg sulfurized 019 calcium phenate, 30 mmoles/kg overbased magnesium sulfonate, 020 5.5~ viscosity index improver, and 22 mmoles/kg product of this 021 invention. (If necessary, additional succinimide was added to 022 bring the total nitrogen content of the finished oil to 2.1%.) ~7~32 o ~ o ~ o o o~
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Claims (27)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for preparing a molybdenum-containing composition which comprises reacting an acidic molybdenum compound and a basic nitrogen compound selected from the group consisting of a succinimide, carboxylic acid amide, hydrocarbyl polyamines, Mannich base, phosphonamide, thio-phosphoramide, phosphoramide, dispersant viscosity index improvers, or mixtures thereof, to form a molybdenum complex wherein from 0.01 to 2 atoms of molybdenum are present per basic nitrogen atom; and reacting said complex with a sulfur containing compound, in an amount to provide 0.1 to 4.0 atoms of sulfur per atom of molybdenum, to form a sulfur- and molybdenum-containing composition.

2. The process of claim 1 wherein said basic nitrogen compound is a succinimide, carboxylic acid amide, hydrocarbyl polyamines, Mannich base, or mixture thereof.

3. The process of claim 2 wherein the sulfur source is selected from the group consisting of sulfur, hydrogen sulfide, phosphorus pentasulfide, R2Sx where R is hydrocarbyl, and x is at least 2, inorganic sulfides or polysulfides, thioacetamide, thiourea, mercaptans of the formula RSH where R is hydrocarbyl, and a sulfur-containing antioxidant.

4. The process of claim 3 wherein the sulfur source is selected from the group consisting of sulfur, hydrogen sulfide, phosphorus pentasulfide, R2S where R is C1-4 hydrocarbyl, and x is at least 3, inorganic sulfides, or polysulfides, thioacetamide, thiourea and RSH where R is C1-40 alkyl, and the acidic molybdenum compounds is selected from the group consisting of molybdic acid, ammonium molybdate, and alkali metal molybdates.

5. The process of claim 4 wherein said sulfur source is selected from the group consisting of sulfur, hydrogen sulfide, RSH where R is C1-10 alkyl, phosphorus pentasulfide, and (NH4)2Sx', where x' is at least 1, said acidic molybdenum compound is molybdic acid or ammonium molybdate, and said basic nitrogen compound is selected from the group consisting of a succinimide, carboxylic acid amide, hydrocarbyl polyamides, and Mannich base.

6. The process of claim 5 wherein said basic nitrogen compound is selected from the group consisting of a C24-350 hydrocarbyl succinimide, carboxylic acid amide, and a Mannich base prepared from a C9-200 alkylphenol, formaldehyde, and an amine.

7. The process of claim 6 wherein said basic nitrogen compound is a polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride and tetraethylene pentaamine or triethylene tetraamine.

8. The process of claim 6 wherein said basic nitrogen compound is a carboxylic acid amide prepared from one or more carboxylic acids of the formula R2COOH, or a derivative thereof which upon reaction with an amine yields a carboxylic acid amide, wherein R2 is C12-350 alkyl or C12-350 alkenyl and a hydrocarbyl polyamine.

9. The process of claim 8 wherein R2 is C12-20 alkyl or C12-20 alkenyl and the hydrocarbyl polyamine is tetraethylene pentaamine or triethylene tetraamine.

10. The process of claim 5 wherein said basic nitrogen compound is a hydrocarbyl polyamine prepared from polyisobutenyl chloride and a compound selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine, and mixtures thereof.

11. The process of claim 6 wherein said basic nitrogen compound is a Mannich base prepared from dodecylphenol, formaldehyde, and methylamine.

12. The process of claim 6 wherein said basic nitrogen compound is a Mannich base prepared from C80-100 alkylphenol, formaldehyde and an amine selected from the group consisting of triethylene tetraamine, tetraethylene pentaamine, and mixtures thereof.

13. The process of claim 1 wherein said reaction is carried out in the presence of a polar promoter.

14. The process of Claim 5 wherein said reaction is carried out in the presence of a polar promoter.

15. The process of Claim 7 wherein said reaction is carried out in the presence of a polar promoter.

16. The process of Claim 1 wherein said reaction is carried out in the presence of a polar promoter which is water.

17. The process of Claim 5 wherein said reaction is carried out in the presence of a polar promoter which is water.

18. The process of Claim 7 wherein said reaction is carried out in the presence of a polar promoter which is water,

19. The product prepared by the process of Claims 1, 5, or 7.

20. The product prepared by the process of Claims 13, 14 or 15.

21. The product prepared by the process of Claims 16, 17 or 18.

22. A lubricating oil composition comprising an oil of lubricating viscosity and from 0.05% to 15% by weight of the product prepared by the process of Claims 1, 5, or 7.

23. A lubricating oil composition comprising an oil of lubricating viscosity and from 0.05% to 15% by weight of the product prepared by the process of Claims 13, 14 or 15.

24. A lubricating oil composition comprising an oil of lubrication viscosity and from 0.05% to 15% by weight of the product prepared by the process of Claims 16, 17 or 18.

25. A lubricating oil concentrate composition comprising an oil of lubricating viscosity and from 15% to 90% by weight of the product prepared by the process of Claims 1, 5, or 7.

26. A lubricating oil concentrate composition comprising an oil of lubricating viscosity and from 15% to 90% by weight of the product prepared by the process of Claims 13, 14, or 15.

27. A lubricating oil concentrate composition comprising an oil of lubricating viscosity and from 15% to 90% by weight of the product prepared by the process of Claims 16, 17, or 18.