SE452017B - SET TO PREPARE A SULFUR AND MOLYBDE-CONTAINING LUBRICANTS ADDITIONAL COMPOSITION, AND LUBRIC OIL COMPOSITION AND LUBRICANE CONCENTRATE COMPOSITION PREPARED AS SET - Google Patents

Description

The compositions described in U.S. Pat. No. 3,9H,866, such as oxymolybdenum diisopropyl phosphorodithioate.

U.S. Patent No. 3,18A A10 discloses certain dithiomolybdenyl acetylacetonates for use in lubricating oils.

Braithwaite and Greene in Wear, U6 (1978) H05-H32 describe various molybdenum-containing compositions for use in engine oils.

U.S. Patent No. 3,3H9,108 teaches a molybdenum tricoxide complex with diethylenetriamine for use as an additive for molten steel.

Russian Patent 533,625 teaches lubricating oil additives made from ammonium molybdate and alkenylated polyamines.

Another way of incorporating molybdenum compounds into oil is to prepare a colloidal complex of molybdenum disulfide or oxysulphide dispersed using known dispersants. U.S. Patent 3,223,625 discloses a process in which an acidic aqueous solution of certain molybdenum compounds is prepared and then extracted with a hydrocarbon ether dispersed with an oil-soluble dispersant and then liberated from the ether. U.S. Pat. No. 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_u aliphatic alcohol, contacting it with a sulfide ion generator and then removing the solution. . Dispersants which are said to be effective in this process are petroleum sulfonates, phenolates, alkylphenolate sulphides, sulfur-treated olefins and combinations thereof. A process for the preparation of a sulfur- and molybdenum-containing lubricant additive composition has now emerged from combining at a temperature sufficient to effect reaction (I) an acidic molybdenum compound selected from molydenic acid, molybdate, sodium molybdate, potassium molybdenum molybdate, potassium metal molybdate 4, MoO2Br2, Mo2O3C16, molybdenum trioxide and other similar acidic molybdenum salts, ammonium-molybdenum hydrogen salts, such as sodium hydrogen molybdate, MoOCl (II) a basic nitrogen compound selected from (i) succinimides prepared from a hydrocarbon hydrocarbyl hydrocarbyl , and dimethylaminopropylamine or an ethyleneamine, the ethyleneamines being ethylenediamine, diethylenetriamine, triethylenetetraamine and tetraethylenepentaamine or the like; (ii) a carboxylic acid amide prepared from (1) a carboxylic acid of the formula R 2 CO 3 H, wherein R 2 represents C 12-20 alkyl or a mixture of this acid with a polyisobytenyl carboxylic acid, wherein the polyisobutenyl group contains from 72 to 128 carbon atoms and (2) a hydrocarbyl polyamine, such as an ethylene amine; (III) a Mannich base prepared by bringing a C 9-20 alkyl-Phenol, formaldehyde or paraformaldehyde and an amine compound selected from methylamine, diethylenetriamine, triethylenetetraamine and tetraethylenepentaamine, wherein the Mannich base is optionally borated; in such a Ratio to provide 0.01 to 2.00 atoms of molybdenum per basic nitrogen atom, (III) a sulfur source selected from sulfur, hydrogen sulfide, phosphorus pentasulfide, R 2 SX, wherein R is hydrocarbyl and x is at least 2, inorganic sulfides, inorganic polysulfides, mercaptans of the formula RSH, wherein R represents hydrocarbyl, thiourea, thioacetamide or a sulfur-containing antioxidant, in such a ratio to provide 1.0 to 2.6 atoms of sulfur per atom of molybdenum.

Lubricating oil compositions containing the prepared additive described herein are effective as either liquid and lubricating grease compositions (depending on the specific additive or additives used) to inhibit oxidation, provide wear-reducing and extreme pressure properties and / or modify the frictional properties of oil, which, when used as a crankcase lubricant, can lead to improved cost per mile. The precise molecular formula of the molybdenum compositions of the present invention is not known with certainty; however, they are believed to be compounds in which molybdenum, the valencies of which are saturated with atoms of oxygen or sulfur, are either complexed with or salted by one or more nitrogen atoms in compositions containing basic nitrogen and used in the preparation of these compositions.

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

By acid is meant that the molybdenum compounds will react with a basic nitrogen compound, which is measured by ASTM test D-664 or D-2896 titration procedure. These molybdenum compounds are typically hexavalent and correspond to the following compositions: molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkaline metal molybdates and other molybdenum salts, such as hydrogen salts, for example sodium hydrogen-molybdenum-molybdate, 4 2 2 '' ra molybdenum compounds. Suitable molybdenum compounds are molybdic acid, ammonium molybdate and alkali metal molybdates. Particularly suitable are molybdenic acid and ammonium molybdate.

The basic nitrogen compound must have a basic nitrogen content, as measured by ASTM D-664_or C-2896. It is suitably oil soluble. Typical such compositions are succinimides, carboxylic acid amides, hydrocarbon polyamines, Mannich bases and mixtures thereof. These basic nitrogen-containing compounds are nitrogen-containing compounds. described below (keeping in mind the reservation that each must have at least one basic nitrogen.) Each of the nitrogen-containing compositions may be post-treated with, for example, boron using procedures well known to those skilled in the art as long as the compositions continue to contain basic nitrogen. are particularly applicable to succinimides and Manních base compositions.

Mono- and polysuccinimides, which can be used to prepare lubricating oil additives described herein, are described in numerous and are well known to those skilled in the art. Certain fundamental types of succinimides and intended materials imid "are taught in U.S. Pat. Nos. 3,219,666, 3,172,892 and 3,272,746. The term" succinimide "embraces many of the amide, the omimidine and amidine species which are also generated by this reaction. However, the predominant product is a succinimide and this term has generally been accepted as meaning the product of a reaction of an alkenyl-substituted succinic acid or anhydride with a nitrogen-containing compound. Suitable succinimides due to their commercial availability are the succinimides prepared from a hydrocarbyl succinic anhydride, wherein the hydrocarbyl group contains from about 24 to about 350 carbon atoms, and an ethylene amine, the ethylene amines being particularly characterized by ethylenediamine, diethylenetriamine, triethylenetriamine and tetraethylene pentamine.

Particularly suitable are the succinimides prepared from polyisobutylene succinic anhydride having 7D to 128 carbon atoms and tetraethylenepentamine or triethylenetetramine or mixtures thereof.

Carboxylamide compositions are also suitable as starting materials for the preparation of the products of the present invention. Typical such compounds are those described in U.S. Patent No. 3,065,064. These compositions are usually prepared by bringing a carboxylic acid or anhydride or ester thereof, having at least 12 to about 350 aliphatic carbon atoms into the substantially aliphatic chain and, if desired, with sufficient protrusion. aliphatic groups to render the molecule oil-soluble, to react with an amine or a hydrocarbyl polyamine such as an ethylene amine, to give a mono- or polycarbocyclic acid amide. Suitable are the amides prepared from (1) a carboxylic acid of the formula R 2 CQQH wherein R 2 represents 10 (j) s 452 017 C 12-20 alkyl or a mixture of this acid with a polyisobutenyl carboxylic acid, wherein the polyisobutenyl group contains from 72 to 128 carbon atoms, and (2) an ethyleneamine, especially triethylenetetramine or tetraethylenepantamine or mixtures thereof.

Another group of compounds useful in the present invention are hydrocarbylamines, preferably of the type described in U.S. Patent No. 3,574,576. Hydrocarbyl, which is suitably alkyl, or olefinic having one or two positions of unsaturated nad, usually contains from 9 to 350, preferably from 20 to 200 carbon atoms. Particularly suitable hydrocarbyl polyamines are those which are derived, for example, by bringing polyisobutenyl chloride and a polyalkylene polyamine, such as an ethylene amine, for example ethylenediamine, diethylenetriamine, tetraethylenepentamine, 2-aminoethylpiperazine, 1,3-propylenediamine, 1,2 -propylenediamine and the like to react.

Another group of compounds useful for providing basic nitrogen are the Mannich base compositions. These compositions are prepared from a phenol or C 9,200 as a formaldehyde or formaldehyde intermediate, such as a paraformalalkylphenol, an aldehyde, a seeds and an amino compound. The amine may be a mono- or polyamine and typical compositions are prepared from an alkylamine such as methylamine or an ethyleneamine such as diethylenetriamine or tetraethylenepentamine and the like. The phenolic material can be sulfur treated and suitably is dodecylphenol or a C80-1010 alkylphenol. Typical Mannich bases that can be used in the present invention are described in U.S. Patent Nos. 838,197 and U.S. Patents 3,669,228, 3,368,972 and 3,539,663.

The latter application describes Mannich bases prepared by reacting an alkylphenol having at least 50 carbon atoms, preferably 50 to 200 carbon atoms, with formaldehyde and an alkylene polyamine HN (ANH) aH, wherein A represents a saturated divalent alkyl hydrocarbon having 2 to 6 carbon atoms and n represents 1-10 and where the condensation product of alkylene polyamine can be further reacted with urea or thiourea. The use of these Mannich bases as starting materials To produce lubricating oil additives can often be significantly improved by treating the Mannich base using conventional methods for introducing boron into the composition. Suitable basic nitrogen compounds for use in the present invention are succinimides, carboxylic acid amides and Mannich bases.

Representative sulfur sources are sulfur, hydrogen sulphide, Phosphorene-1-4 alkyl and x represents at least Z, inorganic sulphides and polysulphides, such as tasulfide RZSX, where R represents hydrocarbyl, preferably C as (NH4) 2Sx, where x represents at least 1, thioacetamide and mercaptan the formula RSH, wherein R is defined as above. Also useful as sulfur treating agents are traditional sulfur-containing antioxidants, such as wax sulfides and polysulfides, sulfur-treated olefins, sulfur-treated carboxylic acids and esters and sulfur-treated ester olefins, and sulfur-treated alkylphenols and the metal salts thereof.

Sulfur-treated fatty acid esters are prepared by reacting sulfur, sulfur monochloride and / or sulfur dioxide with an unsaturated fat ester under elevated temperatures. Typical esters include C 1 -C 20 alkyl esters of C 8 -C 20 unsaturated fatty acids, such as palmitoleic acid, oleic acid, ricinoleic acid, petroselic acid, vaccinic acid, linoleic acid, linolenic acid, oleostearic acid, likanoic acid, paranaric acid, tartaric acid, α-α-acidic acid, . Particularly good results have been obtained with mixed unsaturated fatty acid esters, such as those obtained from animal fats and vegetable oils, such as pine oil, flaxseed oil, olive oil, castor oil, peanut oil, rapeseed oil, fish oil, sperm oil and so on. Examples of fatty esters include lauryl tallate, methyl oleate, ethyl: oleate, lauryl oleate, cetyl oleate, cetyllin oleate, lauryl ricinoleate, o-leyl linoleate, oleyl stearate and alkyl glycerides.

In ester olefins with sulfur crosslinks, such as a sulfur-treated 10-C 25 fatty alkyl or alkenyl alcohols, wherein the fatty acid and / or mixture of C 10 -C 20 olefins with fatty acid esters of C acids and C 1 -C 25 or the alcohol is unsaturated can also be used.

Sulfur-treated olefins are prepared by the reaction of the C5-C6 olefin or a low molecular weight polyolefin derived therefrom with a sulfur-containing compound such as sulfur, sulfur monochloride and / or sulfur dichloride. Also useful are the aromatic sulfides and alkyl sulfides such as dibenzyl sulfide, dixylyl sulfide, acetyl sulfide, diparaffin wax sulfide and polysulfide, cracked wax olefin sulfides and so on. 10 20 25 30 35 40 7 452 017 They can be prepared by treating the starting material, for example olefinically unsaturated compounds, with sulfur, sulfur monochloride and sulfur dichloride. Particularly suitable are the paraffin vacciomers described in U.S. Pat. No. 2 BUS 156.

Sulfur-treated alkylphenols and the metal salts thereof comprise compositions such as sulfur-treated dodecylphenol and the calcium salts thereof. The alkyl group usually contains from 9 to 500 carbon atoms. The metal salt may suitably be a Group I or Group II salt, especially sodium, calcium, magnesium or barium. Suitable sulfur sources are sulfur, hydrogen sulphide, phosphorus pentasulphide, R2Sx, wherein R represents hydrocarbyl, suitably C1-10 alkyl and x represents at least 3, mercaptans, wherein R represents C1-10 alkyl, inorganic sulfides and polysulfides, thioacetamide and thiourea. The most suitable sources of sulfur are sulfur, hydrogen sulphide, phosphorus pentasulphide and inorganic sulphides and polysulphides.

The pole axe promoter suitably used in the process of the present invention is one which facilitates interaction between the acidic molybdenum compound and the basic nitrogen compound. A large number of such promoters are well known to those skilled in the art. Typical promoters are 1,5-propanediol, 1,1-butanediol, diethylene glycol, butylse cellosolv, propylene glycol, 1,1-butylene glycol, methyl carbitol, ethanolamine, diethanolamine, N-methyl-diethanolamine, dimethylformamide, N- methyl acetamide, dimethylacetamide, methanol, ethylene glycol, dimethyl sulfoxide, hexamethylphosphoramide, tetrahydrofuran and water. Suitable are water and ethylene glycol. Water is especially suitable.

While usually the polar promoter is added separately to the reaction mixture, it may also be present, especially in the case of water, as a component of non-aqueous starting materials or as hydration water in the acidic molybdenum compound, such as (NHu) 6Mo7O2u.NH2O . Water can also be added as ammonium hydroxide.

One method of preparing compositions of the present invention is to prepare a solution of the acidic molybdenum intermediate and a basic nitrogen-containing compound suitably in the presence of a polar promoter with or without diluent. Use the diluent; was provided, if desired, to provide a suitable viscosity for easy agitation. Typical diluents are lubricating oil and liquid compounds, which contain only carbon and hydrogen. Optionally, ammonium hydroxide may also be added to the reaction mixture to provide a solution of ammonium molybdate. This reaction is carried out at IEI 452 017 B a temperature from the melting point of the mixture to reflux temperature. It is usually carried out at atmospheric pressure, although higher or lower pressures may be used if desired. This reaction mixture is treated with a sulfur source, as defined above, at an appropriate pressure and temperature for the sulfur source to react with the acidic molybdenum and basic nitrogen compounds. In some cases, removal of water from the reaction mixture may be desirable before completion of the reaction with the sulfur source.

In the reaction mixture, the ratio of molybdenum compound to basic nitrogen compound is not critical; however, as the amount of molybdenum with respect to basic nitrogen increases, the filtration of the product becomes more difficult. Since the molybdenum component is likely to oligomerize, it is advantageous to add as much molybdenum as can be easily maintained in the composition. Usually the reaction mixture will have been added from 0.01 to 2.00 atoms of molybdenum per basic nitrogen atom. from 0, U to 1.0 and most preferably from 0, U to 0.7 atoms of molybdenum per atom of basic nitrogen to the reaction mixture.

The sulfur source is usually added to the reaction mixture in such a ratio, so that 1.0 to 2.6 atoms of sulfur per atom of molybdenum W are provided.

The polar promoter, which is optionally or suitably used, is usually present in the ratio of from 0.1 to 50 moles of promoter per mole of molybdenum. Preferably from 0.5 to 25 and most preferably 1.0 to (75 moles of the promoter are present per mole of the molar volume).

The lubricating oil compositions containing the additives of the present invention can be prepared by mixing by conventional methods the appropriate amount of the molybdenum-containing composition with a lubricating oil. The selection of the particular base oil depends on the intended application of the lubricant and the lubricating oil. The content of other additives In general, the amount of molybdenum in the additive will vary from 0.05 to 15% by weight and, if appropriate, from 0.2 to 10% by weight.

The lace oil which can be used in the present invention comprises a large variety of hydrocarbon oils, such as naphthenic bases, Paffaffin bases, mixed base oils as well as synthetic oils, such as esters and the like. The lubricating oils can be used individually or in combination and generally have a viscosity ranging from 50 to 40 su and usually from 10 to 15 su at 58 ° C. 10 15 20 25 (7 35 9 452 Û17 In many cases it may be advantageous to form concentrates of the molybdenum-containing additive within a carrier liquid; these concentrates provide a suitable method for handling and transporting the additives before their subsequent dilution and use. the concentration of the molybdenum-containing additive within the concentrate can vary from 15 to 90% by weight, although it is convenient to maintain a concentration between 15 and 50% by weight.

The final use of the lubricating oil compositions of the present invention may be in marine cylinder lubricants, such as in cross-flow diesel engines, crankcase lubricants, such as in automobiles and railways, heavy machinery lubricants, such as steel mills and the like, or as greases for bearings and the like. . Whether lubricant fi is a liquid or a solid will usually depend on the presence of a thickener. Typical thickeners include polycarbamide acetates, lithium stearate and the like.

If desired, other additives may be included in the lubricating oil compositions of the present invention. These additives include antioxidants or oxidation inhibitors, dispersants, anti-corrosion agents and so on. Also antifoam stabilizers, anti-staining agents, tackifiers, anti-fouling agents, drop point improvers, anti-mist agents, extreme pressure agents, odor control agents and the like may be included.

Certain molybdenum products which can be prepared by the process of the present invention may also find use in making brake lining materials, in high temperature structural materials, in iron and steel alloys, in cladding metal, in electroplating solutions, such as components for electrodes in electric discharge machines, such as fuel additives. , in making self-lubricating or resistant structures, such as mold release agents, in steel phosphating compositions, in brazing fluxes in nutrient media for microorganisms, in making electrosensitive recording materials - in catalysts for the purification of coal, oil shale, tar sands and Z stabilizers or hardeners for natural rubber or polymers.

The following examples are presented to illustrate the process of the present invention and are not intended to be a limitation of the claims. Example 20 To a 500 ml bottle was added 290 g of a solution of an H5% concentrate in oil of the succinimide prepared from polyisobutenyl succinic anhydride. And tetraethylene pentamine and having an enumerative average molecular weight for the polyisobutenyl group of about 980 and 150 ml of hydrocarbon tins. The mixture was heated to 1200 DEG C. Then, for a period of 5 minutes at 100 DEG to 110 DEG C., a solution containing 28.8 g of molybdenum trioxide dissolved in from 12.9 g of concentrated ammonium hydroxide diluted from 12.9 g of concentrated ammonium hydroxide was added. diluted to 100 ml of water (0.2 l mol of ammonia). The reaction mixture was heated to reflux (approximately 15,500) and kept at this temperature for one hour. Hydrogen sulfide gas was added at 115 ° C. A total of 10 g of hydrogen sulfide was added and then the reaction mixture was washed with nitrogen for one hour at 10 ° C. The mixture was then heated to 155 ° C and kept at temperature for one hour. To the mixture was added 100 ml of hydrocarbon tins and then the mixture was filtered hot through diamtome soil. The product is liberated from luminescence at 16 DEG C. at 2.66 kPa to yield 516.6 g of the product containing,, 9U% molybdenum, 2.77% oxygen, 2.10% sulfur and 1.91% nitrogen.

Examples 2 - 8 A solution of 28.8 g of molybdenum trioxide, dissolved in 0.2 mol of ammonia from 12.9 ml of concentrated ammonium hydroxide and diluted to 100 ml with water, was added dropwise over a period of H5 minutes at 100 to 105 ° C. to a solution of 290 g of the succinimide described in Example 1. The reaction mixture is heated to reflux at approximately 15,500 and kept at this temperature for one hour. The mixture was then heated to 14,000 and U g of sulfur was added. The temperature was increased to reflux at 155 ° C and kept at reflux for one hour.

The temperature was increased until 1650 to 170 DEG C. and maintained for two hours.

To the mixture was then added 100 ml of hot hydrocarbon tin to give approximately 200 ml of solvent in the reaction flask. The mixture was filtered hot through diatomaceous earth and then freed from volatility at 16,000 at 2.33 kPa to give 312.8 g of the product, which contained 5.39% molybdenum, 1.75% nitrogen, 3.50% Syr , 50% sulfur.

Example 5 To a 1 liter bottle was added 290 g of the succinimide, as described in Example 1, and 150 ml of hydrocarbon tins. The reaction mixture was heated to 65 ° C and 28.8 g of molybdenum trioxide and 50 ml of water were added 4552 .mu.l. The temperature was maintained at 65 ° to 70 ° C for 1 1/2 hours, then raised to 150 ° C. After 50 minutes and at 150 ° C, 5 g of elemental sulfur and 50 ml of hydrocarbon tin were added. The temperature was raised to 155 DEG to 160 DEG C. (reflux) over a period of 1/2 hour. Some solvent was removed. and the temperature was increased to 165 DEG to 17000 DEG C. The mixture was kept at this temperature for two hours, to which 50 ml of hydrocarbon tins were added and the mixture was filtered through diatomaceous earth and liberated from yield give 5 .mu.l, 5 g of product, which contained,, 93% molybdenum, 3.59, 3, 88% oxygen, 1.92 x nitrogen on 1, u9 1 sulfur. Example U To a 1-liter bottle was added 290 g succcinimide, as described in Example 1, and 150 ml of hydrocarbon tin, the mixture was heated to 65 ° C and 28.8 g of molybdenum trioxide and 50 ml of water were added.The temperature at maximum temperature at 65 ° C for 1/2 hour was increased to 150 ° C during A mixture of 7 g of elemental sulfur and 100 ml of hydrocarbon tins was added to the mixture. reflux at approximately 155 ° C for H5 min and then the temperature was increased to 165 ° C to 170 ° C and kept there for two hours. To the mixture was added 50 ml of hydrocarbon tins and the reaction mixture was filtered hot through diatomaceous earth. The filtrate was volatile at 160 ° C at 2.66 kps for a yield of 316.5 g of product, which contained 6.55% molybdenum, 3.57% oxygen, 1.86% nitrogen, 2.55% sulfur. .

Example 5 To a 1 liter bottle was added 290 g of the succinimide described in Example 1, 28.2 g of molybdenum trioxide, 50 ml of water and 150 ml of hydrocarbon tins. The reaction mixture was heated to 65 ° C and maintained at this temperature for 1/2 hour. Then 6 g of hydrogen sulfide were added at 65-65 ° C for a period of 15 minutes. After addition, the temperature was maintained at 63-65 ° C for one hour with vigorous stirring and under a nitrogen atmosphere. The temperature then rose to 100 ° C to remove most of the water and then to 155 to 160 ° C and was kept at reflux for one hour. The mixture was filtered hot through diatomaceous earth and then evaporated at 160 ° C at 2.66 kPa to yield 31U, 15 g of product, which contained 5.8? % molybdenum, 3.6H oxygen, 2.05 É nitrogen, 0.75% sulfur and 0.08% sediment, 10 20 35 h fi 4f52 0'17 Example 6 12 To a 1 liter bottle was added 290 g of the succinimide described in Example 1 and 150 ml of hydrocarbon tins The reaction mixture was heated to 65 ° C and 28.8 g of molybdenum trioxide and 50 ml were added.The temperature was maintained at 65 ° C for 1/2 hour and rose slowly to 155 ° C at 120 ° C, 10 g of elemental sulfur was added and the reaction mixture was then distilled at 155 ° C for 30 minutes, 160 ° C for 15 minutes, 170 ° for 30 minutes, 175 ° for 30 minutes then 180 ° for 30 minutes. then 120 ml of hydrocarbon tins were added and the reaction mixture was filtered through diatomaceous earth and the filtrate was evaporated at 160 ° C at 2.66 kPa to yield a product containing 5.70% molybdenum, 2.88% oxygen, 1.83% nitrogen and 2.9ß% sulfur.

Example 7 To a 3-liter flask were added 160 g of succinimide, as described in Example 1, and 800 ml of hydrocarbon tins. The reaction mixture was heated to 65 ° C and 200 ml of water and 116 g of MoO 3 were added. The temperature was raised to reflux (98 ° C) and kept at this temperature for 2-1 / 2 hours, until the solution turned clear green. Water was removed up to a temperature of 1H0 OC (bottom). Then 60 g of sulfur was added. The temperature was raised to 155 ° C for a period of 15 minutes and kept at this temperature for 1/2 hour. The temperature was then raised to 180 ° C for a period of 50 minutes and maintained at this temperature for 3-1 / 2 hours. The mixture was then cooled and left overnight. Then, 200 ml of hydrocarbon inner solvent was added and the solution was heated to 150 ° C. It was then filtered through diatomaceous earth and evaporated at 200 DEG C. at 2.66 kPa to yield 287 g of product, which contained H, H9% sulfur, 5.82% molybdenum and 2.58% oxygen.

Example 8 To a 3-liter flask was added 160 g of a polyamide prepared from a C18 carboxylic acid and tetraethylene pentaamine containing 6.29% nitrogen and 800 ml of hydrocarbon tins. The mixture was heated to 55 ° C and 200 ml of water and 116 g of MoO 3 were added. The temperature was raised to reflux, approximately 95 ° C, and maintained at this temperature for U hour, until the solution turned clear green. The solvent was removed at 150 ° C maximum and the mixture was then cooled to 10 ° C and 28 g of sulfur was added. again at 175 DEG C. for a period of 20 minutes and then kept between 175 DEG and 180 DEG C. for 2 hours, the mixture was cooled and left overnight and then 200 ml of hydrocarbon solvent were added. Example 10 13 452 017 The mixture was heated to 130 ° C, filtered through diatomaceous earth and then freed from volatility at 180 ° C bottoms at 2.66 kPa to yield 282 g of product, which contained 5, 5% nitrogen, 2.15% sulfur, 5 51% molybdenum and 5.73% oxygen.

Example 9 To a 1 liter bottle was added H00 g of the reaction isoduct of poly isobutylene chloride, wherein the polyisobutylene group has a numerical average molecular weight of 1 H00 and ethylenediamine in a hydrocarbon solvent. The mixture was released from volatility at 160 OC bottoms and 2.66 kPa and cooled to yield 289 U of product, which contained 1.58% nitrogen. To this were added 200 ml of hydrocarbon tins, 50 ml of water and 29 g of MoO3. The mixture was stirred at reflux approximately 101 ° C for 2 hours and then evaporated at 10 ° C bottoms. Then 7 g of sulfur was added and the temperature was raised to 155 ° C for a period of 10 minutes and kept at this temperature for 1/2 hour. The temperature then rose to 180 ° C for a period of 10 minutes and was maintained at 180 DEG to 185 DEG C. for 2 hours. The mixture was cooled and 100 ml of hydrocarbon tins were added. The mixture was then filtered through diatomaceous earth and after the addition of 100 g of neutral lubricating oil, it was freed from volatiles at 180 OC bottoms and 2.66 kPa to yield NO9 g of product in exchange. k-SS To a 1 liter flask was added 290 s of a Manni ° h ~ baS, prepared from dodecylphenol, methylamine and formaldehyde and having an alkalinity value of 110 and containing 2.7% nitrogen and 200 ml of hydrocarbon. down. The mixture was heated to 65 ° C and 50 ml of water and 29 molybdenum trioxide were added. The mixture was stirred at reflux, 10 h 0 to 110 ° C for H - 1/2 h. The solution got a clear dark brown color and was then freed from volatility at 175 ° C bottoms. The mixture was cooled to 80 DEG C. and 7 g of sulfur were added. was increased to 3111 155 OC for a period of 7 minutes and kept at this temperature for 1/2 hour. The temperature was then raised to 180 ° C for 10 minutes and held for 2 hours. The mixture was then cooled and left overnight. The next day, 100 ml of the temperature was added for a time hydrocarbon solvent. The mixture was heated to 100 ° C and filtered through diatomaceous earth and liberated from volatility at 180 ° C at 2.66 kPa to yield 517 g of pPOdukÉ. 10 20 25 35 H0 452 017 1 ”Example 11 To a 3-liter bottle was added 160 g of succinimide as described in Example 1 and 800 ml of hydrocarbon tins. This mixture is heated to 65 ° C and then 116 ml of Msoñ are added with water. The mixture was stirred at reflux (96 ° C) for 2 hours. It was cooled and an additional 116 g of MOOB was added. The mixture was stirred at reflux (97 ° C) for 10 hours. The mixture was cooled and allowed to stand overnight. It is then freed from volatility at 180 DEG C., cooled to 100 DEG C. 60 g of sulfur are added. The temperature was then increased to 155 ° C for a period of 15 minutes and kept at this temperature for 1% for 2 hours and then heated to 180 ° C for a period of 15 minutes and kept at this temperature for 3 hours. The mixture was cooled and 200 ml of hydrocarbon tins were added. The solution was heated to 130 E90 and filtered through diatomaceous earth with the addition of hydrocarbon tins to aid in filtration. The filtrate was liberated from volatility at 200 DEG C. and 2.66 kPa to yield 13.25 g of product.

Example 12 (B-3721-H9) \ To a 1 liter bottle was added N00 g of the hydroxylcarbylpolyamine described in Example 9, which was freed from volatility at 160 ° C at 2.66 kPa and then 200 ml of hydrocarbon tins, 50 ml of water and 29 g MoO3. The mixture was stirred at 1 ° C for 1 hour and then heated to 10 ° C to remove water. Sulfur (7 g) was added and the temperature was gradually increased to 180 - 185 ° C, where it was kept for 2 hours. After cooling, 100 ml of hydrocarbon tins were added and the mixture was filtered through diatomaceous earth and freed from volatility at 180 ° C and 2.36 kPa to yield H09 g of product containing Mo U, 67 2 (neutron activity), U, 95 (X-rays fluorescence); O, l§7%; S, 1.9ü%.

Example 1a To a 1-liter flask, which at 65 ° C contained 289 e of volatility liberated the polyamine described in Example 12, and 200 ml of hydrocarbon tins, were added 50 ml of water and 29 g of MoO5. The mixture was stirred at reflux for 2 hours and then freed from volatility at 175 ° C. After cooling to 110 - 115 ° C, 10 g of Has was added. then the mixture was heated to 155 - 160 g C and kept for 1 tlm.

After cooling, 75 ml of hydrocarbon tins were added and the mixture was filtered through diatomaceous earth. Neutral oil (100 g) was added and the mixture was freed from volatile at 180 ° C at 2.66 kPe to give a yield of H12 g of product containing N, 0.90%; S, 2.31%; Mo, u, 21 (N.A.), 4.67 (xRF); o, 1.01. 10 / N 15 20 25 H0 15 452 017 Exemoel lü To a 1-liter flask containing 500 g of borated Mannich base prepared from a CBn-10O alkylphenol, formaldehyde and tetraethylenepentamine or triethylenetetraamine or mixtures thereof containing urea ( Amoco 9250Y) and 200 ml of hydrocarbon tins at 65 ° C were added U0 ml of water and 25 g of MoO3. The mixture was stirred at reflux for N15 hours and then freed from volatility at 165 ° C. After cooling to 10 DEG C., sulfur was added and the temperature was gradually increased to 185 DEG C., where it was kept for 2 hours. Then 75 ml of hydrocarbon tins were added and the mixture was filtered through diatomaceous earth and then freed from volatility at 180 ° C at 2.66 kPa to yield 307 g of product containing N, 1.04%; S, 2.53%; Mo, u, 68% (N.A.), ”, 99% (N.A.), 4.99% (xRF); o, 2.53%, B, o, 22 z.

Example 15 'To a 3 liter flask was added 500 g of a concentrate of polyisobutenyl succinic anhydride, wherein the polyisobutenyl group had a numerical average molecular weight of about 980, and the methylaminopropylamine. The temperature of the reaction mixture was raised to 160 ° C, kept therein for 1 hour and then freed from volatility at 170 ° C at 2.66 kPa. To this mixture were added 350 ml of hydrocarbon tins, 50 ml of water and 29 g of MoO5. This mixture was stirred at reflux for 2 hours and then quenched at 10 ° C to remove water. Then 7 g of sulfur were added and the mixture was kept at 180 - 185 ° C for 2 hours. After cooling, additional hydrocarbon tins were added and the mixture was filtered through diatomaceous earth and then evaporated at 180 ° C at 2.66 kPa to yield 536 g of product containing N, 1.17%; S, 1.55%; - no, 3.37% (N.A.), 3.31%; o, 2.53%.

Example 1 To a 1 liter flask containing 290 g of succinimide, as described in Example 1, and 200 ml of hydrocarbon tins at 65 DEG C. was added 50 ml of water. The mixture was stirred at reflux for 1.5 hours and then stirred at 165 ° C to remove water. After cooling OC, H0 g of butyl disulfide was added and the mixture was heated at 185 DEG C. for 2.5 hours. Then an additional 100 ml of hydrogen tin was added before filtration through diatomaceous earth and the mixture was evaporated at 180 ° C at 2.66 Rea to give in one yield 305 g of product containing w, 1.92%; s, 0.47%; mo, 6.21% (mm, 6.51 »ß (men o, u, 19).

To a 1-liter flask containing 290 g of succinimide described in Example 1 and 200 ml of hydrocarbon tins was added at 75 ° C 50 ml of water and 29 g of MOO3. The mixture was refluxed for 1.5 hours and then evaporated at 200 ° C to remove water. After cooling to 100 DEG C., 19 g of thioacetamide were added and the mixture was gradually heated to 200 DEG C., where it was kept for 0.75 hours. Then 150 ml of hydrocarbon tins were added and the mixture was filtered through diatomaceous earth and evaporated at 180 DEG C. at 2.66 kPa to give in exchange a product, which contained N, 1, n6 z; s, 2.05%; Me, u, 57% (N.A.), u, 7o z (xRF); 0, 2.38%. Prior to testing, dilute this product with 100 g of neutral lubricating oil.

Example 18 To 292 g of the starting material described in Example 13 were added 200 ml of hydrocarbon tins, 50 ml of water and 33.5 g of ammonium paramolybdate. The mixture was refluxed for 2 hours and then evaporated to remove water. After cooling to 10 00, 7 g of sulfur was added. The mixture was heated to 180 - 185 ° C and kept for 2 hours. After adding 100 ml of hydrocarbon tins, the mixture was filtered through diatomaceous earth. Neutral diluent oil (100 g) was added and the mixture was evaporated at 180 DEG C. at 2.66 kPa to give in exchange Mlu2 g of product containing N, 0.92%; S, 2.02%; Mo, n, 57% (N.A.), u, 60% (XRF); o, 1.37%.

Example 19 To a 3-liter flask containing 160 g of the succinimide described in Example 1 and 800 ml of hydrocarbon tins at 75 ° C were added 200 ml of water and 116 g of MoO 5. The mixture was refluxed for 3 hours and then evaporated at 180 DEG C. to remove water. At 110 ° C, about 6U g of H28 was added. Additional hydrocarbon tins (200 ml) were added and the mixture was filtered through diatomaceous earth and then evaporated at 180 DEG C. at 2.66 kPa / l to yield 1,290 g of product containing N, 1.85 l; s, u.2u%; Me, 5.92 (N.A.), 5.83% (XRF), 0.12%.

Example 20.

To a 1-liter flask containing l l60 g of succinimide described in Example 1 a Boo mi keivätte chinner at 75 ° c was added zoo mi å fl å water and 116 g MOO3. The mixture was stirred at reflux for 5 hours and then heated to 186 ° C to remove water. After cooling to 110 ° C, 35 É H25 was added. The mixture was heated to 182 ° C, then 200 ml of hydrocarbon tins were added and the mixture was filtered through diatomaceous earth. Evaporation at 180 DEG C. at 2.66 kPa gave in yield 12.72 g of product, which contained N, 1.93%; S, 3.20%; Mo, 5.90% (N.A.); 0.3-01%.

Example 21 10 ao 25 C g 35 HO 17 452 017 To a 1 liter bottle containing 290 g of the succinimide described in Example 1 and 200 ml of hydrocarbon tins at 75 ° C was added 50 ml of water and 29 g of MoO 3. The mixture was stirred at reflux for 1.5 hours and then heated to 187300 to remove water. Then, 10 ml of hydrocarbon tins and at 175 DEG C. BH g were added aqueous ammonium polysulfide (51% free sulfur). This material was slowly heated to 180 ° C and held there for 2.25 hours. It was produced by diatomaceous earth and stripped at 180 DEG C. at 2.66 kPa to give in exchange 318 g of product containing N, 1.89 Z; S, u.o7 "%; ke, 6.l6% (N.A.).

Example 22 To a 1 liter bottle containing 290 g of succinimide, described in Example 1, and 200 ml of hydrocarbon tins at 75 ° C was added 50 ml of water and 29 g of MoO 3 and then heated at 195 ° C to remove water. After cooling to 70 ° C, 58 g of a 52-60% technical solution of ammonium sulfide were added. The reaction mixture was heated to 180-185 ° C for U h. After cooling to 115 ° C, 125 ml of hydrocarbon tins were added and the mixture was filtered through diatomaceous earth and then evaporated at 180 ° C at 2.66 kPa to yield 518 g of the product, which contained 6.19% ne (xRF>).

Example 23 To a 1 liter bottle containing 330 g of a concentrate,. This mixture was refluxed for 3 hours containing 1.50% N in oil of a polyisobutenylsuccinimide prepared from triethylenetetraamine and a polyisobutenylsuccinimide prepared from triethylenetetraamine and a polyisobutenylsuccinimide; wherein the polyisobutenyl group has a numerical average molecular weight of 980 and 200 ml of hydrocarbon tins at 75 ° C was added 50 ml of water and 22 gMoO5. This mixture was stirred at reflux (about 100 ° C) for 11 hours. It was then heated to 180 ° C to remove water. After cooling to 10 DEG C., 9 g of sulfur were added and the mixture was slowly heated to 180 DEG C., where it was kept for 5 hours. After the addition of 100 ml of hydrocarbon tins, the mixture was filtered through diene -enejora een evaregs custom at 180 ° C at 2.66 kg for a 1 yield see 5%? g product, which contained Me, fl, 15% (N.A.), 3.98% (xRF); N, 1.1 H2 z; s, 2.66%; o, 2.85% (N.A.). šieaesl fi To 291 g of the starting material used in Example 15 and 200 ml of hydrocarbon tins at 75 ° C were added 50 ml of water and 29 g of MoO 5.

The mixture was stirred at reflux for 3 hours and then heated to 50 ° C to remove water. After cooling to 100 DEG C., 15 g of sulfur were added and the mixture was gradually heated to 180 DEG-175 DEG C., where it was kept for 2.5 hours. After adding about 20 ml of hydrocarbons, the mixture was filtered through diatomaceous earth and then 100 g of neutral diluent oil were added. Evaporation at 200 DEG C. at 2.66 kPa gave in exchange H10 g of product containing Mo, 4.68% (NA) - Example 25. To a 1-liter flask containing H7 g of tetraethylene pentaamine was added NOR g of polyisobutenyl succinic anhydride with a PIBSA number of 76.7. The mixture was heated to 150 DEG-160 DEG C., where it was kept for 1.5 hours. It was stripped off at room temperature at 2.66 DEG C. for a yield of 39 g of polyisobutenyl succinamide. To this succinimide was added 300 ml of hydrocarbon solution, 135 ml of water and Bo g mooš. The mixture was stirred at reflux for 6.5 hours and then heated to 1800 DEG C. to remove water. After cooling to 100 DEG C., H1 g of sulfur was added and the temperature was gradually increased to 180 DEG-185 DEG C., where it was kept for 100 hours. After adding 200 ml of hydrocarbon tins, the mixture was filtered through diatomaceous earth and then dried at 200 ° C at 2.66 kPa and 300 g of neutral oil were added to yield 810 g of product containing 6.23% Mo with XRF.

Example 26 'Me To a 1 liter flask containing 290 g of the succinimide described in Example 1 and 200 ml of hydrocarbon tins at 75 ° C was added 50 ml of water and 29 g of MoO 3. The mixture was stirred at 96-98 ° C for 2-1 / 2 hours and possibly stirred at 191 ° C. after cooling to 75 ° C, 3 ml of 1-butantol was added and the mixture was brought to reflux for 1 hour. The mixture was then evaporated at 180 ° C at 2.66 kPa to yield 318 g of product, which contained Mo 6.17% (XRF); N, 1.97%: S, 1.05%.

Example 27 Lubricating oil compositions containing additives prepared in accordance with the present invention have been tested in a variety of tests. Reported below are the results of certain tests, which are described as follows. In the oxidizer B test, the stability of the oil is measured by the time required to consume one liter of oxygen per 100 g of test oil via 172 ° C; in the current test 25 g of oil were used and the result is corrected to a 100 g sample. The catalyst used at a rate of 1.58 cm / s per 100 cm 3 of oil contains a mixture of soluble salts providing 95 ppm of copper, 80 ppm of iron, N, 8 ppm of manganese, 100 ppm of lead, U9 ppm of tin. Results 8? This experiment is reported as hours for consuming 11 l of oxygen and measuring the oxidative stability of the oil. fi z fifi rvfff-'n-u-nn The anti-corrosion properties of the compositions can be tested by their performance in the CRC L-38 bearing corrosion test. In this test, separate strips of copper and lead are immersed in the test lubricant and the lubricant is heated for 20 hours at a temperature of 1H6 OC. The copper strip is weighed and then washed with potassium cyanide solution to remove E copper compound deposits. It is then weighed again. The weight losses Ü of the two strips are reported as a measure of the degree of corrosion caused by the oil.

The copper strip test is a measure of the corrosivity to non-ferrous metals and is described in ASTM Test Method D-130. Wear-reducing properties are measured through the H-ball abrasion and U-ball welding tests. The Ä-ball abrasion test is described in ASTM D-2266 and is run at 5U OC for 30 minutes using steel balls and a HO kg weight and the 4-ball welding test is a variation of the ASTM D-2783 test at ambient temperature until the point of intersection with weights was reduced. by 5 kg, until the appropriate load is determined. The coefficient of friction of the lubricating oils containing additives of the present invention was tested in the Kinetic Oiliness Testing Machine (KOTM) manufactured by G.M. Neely of Berkeley, California. The method used in this experiment is described by G.L. Neely, Proceeding of Mid-Year Meeting, American Petroleum Institute 1932, pp. 60-7U in ASLE Transactions, vol. 8, pp. 1-11 (1965) and ASLE Transactions, vol. 7, page ZH-31 (196A). The coefficient of friction was measured under limit conditions at 150 ° C and ZOH 0 ° C using 1 kg load and a molybdenum-filled ring on a cast iron plate. Data for some of the test runs for the compositions of the present invention are reported in the table below Unless otherwise indicated, the tested formulation in a neutral lubricating oil contained 3.5% of a 50% concentrate of polyisobutenyl succinimide, 20 mmol / kg sulfur treated calcium phenolate, mmol / kg overbased magnesium sulfonate, 5.5% viscosity index improver and 22 mmol / kg product of the present invention (if necessary, additional succinimide was added to bring the total nitrogen content of the finished oil to 2.1%). 20 452 017 1015 ... mno fl ø oro nn O owo 0 Hwo.Q 0oH.om = oo mm @ .0 H @ oo mo: ON 3.5 ..., I. ... Én .ïa..É..n .n_l. ~ ed «3 Uoom fl o fl HQH nnH \ mH Nm fi QH Hm ~ \ n ~ NH fi m ~ \ pH Qcw fi0fl @« woxw: o fl »x fl» m onH | a 12 .. L _. = .rg .df-.H:. mw fl o fl mnßmmc o.m fi m.mH nw ~ mH ~ ~, Hm wE.:o wm | q 2 pcmoomQpx fi> oß fi mm fi mm fl mn fi mß fl mm fi mma mm fl ONH QQH mm fi ow fl wx Q mw> N «m B mw B > ompmwp wc fl cwnßucwønæ fl oz w n fl> umuwmu wc fl cwpnwcmunæ fl os n © fi> ømummu mc fl cwmnwcwunæ fi oz ~ mo mm.om = .on = .o ~ = _o EE wwmmsü 2Bw n ~ nn ~ Ln ~ on ~ Ln ~ Ln ~ Ln : .oH o.H fi w. flfifi. mH @ ^ mm Loum fifi xo m NH om mm: N mm NN, Hm om m fl æ fi NH m fl m fi: H na »mo wmo mno nno Nmo fi no ono mmo wmo ßmo wmo mmo: No mmo mmo fl mo omo mao æ fl o ß fl o o fi o m fl o: Ho n fi o WHO fi ao o fi o moo æoo moo mom: oo Neo H00

Claims (11)

452 017 í- 21 Eatentkrav Process for the preparation of a sulfur- and molybdenum-containing lubricant additive composition, characterized in that at a temperature sufficient to effect reaction (I), an acidic molybdenum compound selected from molybdenic acid, ammonium molybdate, sodium molybdate, potassium molybdate, potassium molybdenum hydrogen salts, such as sodium hydrogen molybdate, HoOCl 4, MoO 2 Br 2, Mo 2 O 3 Cl 5, molybdenum trioxide and other similar acidic molybdenum salts, (II) a basic nitrogen compound selected from (i) succinimides prepared from a hydrocarbyl hydrocarbyl carbon atoms, and dimethylaminopropylamine or an ethyleneamine, the ethyleneamines being ethylenediamine, diethylenetriamine, triethylenetetraamine and tetraethylenepentaamine or the like; (ii) a carboxylic acid amide prepared from (1) a carboxylic acid of the formula R 2 COOH, wherein R 2 represents C 12-20 alkyl _W or a mixture of this acid with a polyisobutenyl carboxylic acid, wherein the polyisobutenyl group contains from 72 to 128 carbon atoms and (2) a hydrocarbyl polyamine such as an ethyleneamine; (iii) a Mannich base prepared by bringing a C 9-200 alkylphenol, formaldehyde or paraformaldehyde and an amine compound selected from methylamine, diethylenetriamine, triethylenetetraamine and tetraethylenepentaamine, wherein the Mannich base is optionally borated; in such a ratio to provide 0.01 to 2.00 atoms of molybdenum per basic nitrogen atom, (III) a sulfur source selected from sulfur, hydrogen sulfide, phosphorus pentasulfide, RQSX, wherein R represents hydrocarbyl and x represents at least 2, inorganic sulfides, inorganic polysulfides. mercaptans of the formula RSH, wherein R represents hydrocarbyl, thiourea, thioacetamide or a sulfur-containing antioxidant, in such a ratio to provide 1.0 to 2.5 atoms of sulfur per atom of molybdenum. Process according to Claim 1, characterized in that the sulfur source represents sulfur, hydrogen sulphide, phosphorus pentasulphide, R 2 SX where R represents C 1-4 hydrocarbyl and x 452,017 za. represents at least 3, inorganic sulphides or inorganic polysulphides, thioacetamide, thiourea or RSH where R represents a C 1-4 alkyl and the acidic molybdenum compound is molybdic acid, ammonium molybdate or alkali metal molybdates. Process according to Claim 2, characterized in that the sulfur source is sulfur, hydrogen sulphide, RSH, where R represents C 1-1 alkyl, phosphorus pentasulfide, or (NH 4) 2 Sx ', where x' represents at least 1, the acidic molybdenum compound is molybdic acid or ammonium molybdate and the basic nitrogen compound is a succinimide, carboxylic acid amide, hydrocarbyl polyamines or Hannich base. IN 4. A process according to claim 3, characterized in that the basic nitrogen compound represents a C24-350 hydrocarbylsuccinimide, carboxylic acid masmid or a Mannich base prepared from a C9-22 alkylphenol, formaldehyde and an amine. 5. A process according to claim 4, characterized in that the basic nitrogen compound is a polyisobutenylsuccinimide prepared from polyisobutenylsuccinic anhydride and tetraethylenepentamine or triethylenetetraamine. Process according to Claim 4, characterized in that the basic nitrogen compound is a carbocyclic acid amide prepared from one or more carboxylic acids of the formula R , and a hydrocarbyl polyamine. 7. A process according to claim 6, characterized in that R 2 represents C 12-20 alkyl and the hydrocarbyl polyamine is tetraethylene pentaamine or triethylenetetraamine. Process according to Claim 4, characterized in that the basic nitrogen compound is a Mannich base prepared from dodecylphenol, formaldehyde and methylamine or in that the hazardous nitrogen compound is a Mannich base prepared from C 80-1010 alkylphenol, formaldehyde and triethylene tetraamine or tetraethylene pentaamine or mixtures thereof. Process according to Claim 1, 2, 3, 4, 5, 6, 7 or 8, characterized in that the reaction is carried out in the presence of a polar promoter, preferably water. 10. A lubricating oil composition, characterized in that it comprises an oil having a lubricant level and from 0.05 to 15% by weight of the additive composition prepared according to any one of claims 1-9. 11. A lubricating oil concentrate composition, characterized in that it comprises an oil having an lubricating viscosity and from 15 to 90% by weight of the permissible composition prepared according to any one of claims 1-9.