RU2814015C2 - Less corrosive organo-molybdenum compounds as additives for lubricating oils - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a molybdate ester represented by the following formula:

.

In said formula: R¹ represents a hydrocarbon chain containing from 11 to 21 carbon atoms, R² represents either a hydrogen atom or a hydrocarbon chain containing from 1 to 20 carbon atoms, and m and n independently range from 1 to 5. Also disclosed is a compound used as an additive to lubricating oil, lubricating compositions and a method of producing a molybdate ester.

EFFECT: disclosed molybdenum compound is effective when used in a lubricating composition in an amount sufficient to create a concentration of about 50–5000 mln^-1 of molybdenum in the lubricating composition, with respect to reducing friction and wear, at the same time providing improved protection against copper and lead corrosion.

9 cl, 7 tbl, 15 ex

Description

BACKGROUND OF THE ART

Field of technology to which the invention relates

The present invention relates to the development of less corrosive, high performance organomolybdenum compounds with applications as lubricating oil additives. Lubricating oils containing these compounds have demonstrated improved performance in terms of friction reduction, wear protection, and copper and lead corrosion, particularly for use in diesel and passenger car engine oils that require high performance, longer lasting oxidation additives. and hydrolytic stability.

The class of compounds in the present invention can be represented by the following formula:

where R ¹ represents a hydrocarbon chain, and R ² represents either a hydrogen atom or a hydrocarbon chain. The R ¹ group is composed of an unsaturated and/or saturated and/or branched hydrocarbon chain containing from 1 to 21 carbon atoms. Preferably, the R ¹ group is unsaturated or branched. In addition, it is preferable that the R ¹ group is both saturated and branched. It is also preferable that R ¹ be composed of a hydrocarbon chain containing from 11 to 21 carbon atoms. The R ² group may represent a hydrogen atom or a linear, cyclic or branched hydrocarbon chain containing from 1 to 20 carbon atoms. The number of methylene spacer groups ( n and m ) in each case is independently from 1 to 5. It is preferable that the number of methylene spacer groups ( n and m ) in each case is independently 2 or 3.

Preferred organomolybdenum compounds are prepared by the reaction of either N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]-ethyl]oleamide or N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl) amino]ethyl]isostearamide, with a molybdenum source, and are effective for use as lubricating oil additives in passenger car motor oils and heavy duty diesel engine oils, at dosages in the range of 0.05-5.00 weight percent.

Prototype discussion

Patent document GB796732 describes the preparation of organo-molybdenum compounds as a reaction product of an alpha- or beta-alkanediol and a source of molybdenum, and the use of these compounds as corrosion inhibitors and antioxidants in lubricating oil compositions primarily derived from mineral oils. The compounds of the class of the invention are chemically different and do not belong to the class described in patent document GB796732. In addition, patent document GB796732 does not discuss the described examples with respect to their role in terms of improving frictional characteristics and/or wear protection.

Patent document US20170044456 describes a lubricant composition that is less corrosive to copper and lead for use in heavy duty diesel engine oil formulations that allows the use of an organomolybdenum compound. The lubricant composition discussed in patent document US20170044456 is a copper-lead anti-corrosion solution composition comprising a combination of a sulfur-free organomolybdenum compound, a sulfur-containing organomolybdenum compound and a specific triazole-based corrosion inhibitor. The invention presented herein differs significantly in that the inventive examples represent additives that are inherently less aggressive to copper and lead than comparative organic and/or organometallic additives.

Examples of ligands used to prepare compounds of this class are given in patent documents DE1061966 and JP35012097. However, neither patent document DE1061966 nor patent document JP35012097 describes any subsequent reactions of these ligands with any metals, including molybdenum. In addition, there is no discussion of options for preparing examples of both unsaturated and branched N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-alkylamides, nor the class of organomolybdenum compounds in the present invention based on ligands , representing N -[3-[(2,3-dihydroxypropyl)(3-alkoxypropyl)amino]propyl]-alkylamides. In addition, neither DE1061966 nor JP35012097 discusses applications for examples related to the inventive class of compounds in lubricating oils as friction modifying or wear protection additives.

Patent document DE 1061966 describes the preparation of 2,3-dihydroxy compounds relevant to the ligands of the present invention by reacting an alkylamide intermediate, N -[2-[(2-hydroxyethyl)amino]ethyl]-, with α-chlorohydrin or epichlorohydrin. This method may require the use of caustic bases and creates halogenated waste. In the invention presented herein, the amine intermediates of the alkylamides are instead reacted with glycidol in the presence of ethanol. These reactions are favorable from the point of view of economical use of all atoms, and do not create waste. Ethanol can be isolated from the reaction mixtures by simple distillation and reused in the process.

SUMMARY OF THE INVENTION

Traditional organic friction modifiers, such as glycerol monooleate, are sensitive to both oxidation and hydrolysis when used as additives in motor oil applications. As a result, such additives and their degradation products can lead to operational erosion and/or corrosion (i.e., copper and/or lead). The invention disclosed herein matches or exceeds the friction reduction levels of traditional additives while providing significant improvements in copper and lead corrosion as determined by the Standard Test Method for Evaluation of Corrosiveness of Diesel Engine Oil at 135 °C (HTCBT)) according to ASTM D6594. In addition, organomolybdenum compounds are multifunctional lubricating oil additives that provide improved antioxidant activity, friction reduction and wear protection.

Based on the friction performance, wear and corrosion test results set forth below, inventive examples have been demonstrated to represent a new class of additives capable of matching or exceeding the friction performance and wear resistance of traditional additives while reducing the severity of observed copper corrosion. and lead. This class of compounds according to the invention is particularly useful in both passenger car engine oils and when used in heavy duty diesel engine oils where a high performance, longer lasting friction modifier and/or anti-wear additive is required in terms of oxidative and hydrolytic stability.

The class of compounds according to the invention can be prepared according to the following General Reaction Scheme:

In the first step, a carbonyl group-containing compound, such as a carboxylic acid, carboxylic acid ester, or triglyceride, is reacted with a mixed primary/secondary amine compound to form a secondary amide. In the second stage, the secondary amide as an intermediate is further reacted with glycerol to obtain a 2,3-dihydroxypropyl adduct. The second step can be carried out in the presence of a protic solvent such as methanol or ethanol to improve the efficiency of the reaction. In the third step, the glycidol adduct is reacted with a molybdenum source, such as molybdenum trioxide, in the presence of water. The reaction mixture containing the molybdenum complex can be diluted with process oil to form the final organomolybdenum product.

As outlined above, the class of compounds of the present invention can also be described as reaction products of an organic ligand and a molybdenum source, carried out in the presence of water. The product containing an organomolybdenum compound can be diluted with process oil. The relative ratios of organic ligand, molybdenum source and process oil can be varied such that the final organomolybdenum product contains between 0.5 and 15.0% molybdenum by weight. More preferably, the organomolybdenum product contains between 2.0 and 10.0% molybdenum by weight. The organic ligand can be described as the reaction products of a carboxylic acid or ester or triglyceride, a mixed primary/secondary amine compound and glycidol. Non-limiting examples of the organic ligand used to prepare the organomolybdenum compounds of the present invention include the following:

N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-lauramide

N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-myristamide

N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-palmitamide

N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-stearamide

N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-isostearamide

N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-myristolamide

N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-palmitoleamide

N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-oleamide

N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-linoleamide

N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-lauramide

N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-myristamide

N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-palmitamide

N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-stearamide

N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-isostearamide

N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-myristoleamide

N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-palmitoleamide

N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-oleamide

N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-linoleamide

N -[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]-lauramide

N -[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]-myristamide

N -[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]-palmitamide

N -[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]-stearamide

N -[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]-isostearamide

N -[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]-myristoleamide

N -[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]-palmitoleamide

N -[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]-oleamide

N -[3-[(2,3-dihydroxypropyl)(3-butyloxypropyl)amino]propyl]-linoleamide

N -[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]-lauramide

N -[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]-myristamide

N -[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]-palmitamide

N -[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]-stearamide

N -[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]-isostearamide

N -[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]-myristoleamide

N -[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]-palmitoleamide

N -[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]-oleamide

N -[3-[(2,3-dihydroxypropyl)(3-octyloxypropyl)amino]propyl]-linoleamide

N -[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]-lauramide

N -[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]-myristamide

N -[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]-palmitamide

N -[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]-stearamide

N -[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]-isostearamide

N -[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]-myristoleamide

N -[3-[(2,3-dihydroxypropyl)(3-decyloxypropylamino]propyl]-palmitoleamide

N -[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]-oleamide

N -[3-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]propyl]-linoleamide

N -[2-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]ethyl]-oleamide

N -[3-[(2,3-dihydroxypropyl)(2-decyloxyethyl)amino]propyl]-oleamide

N -[2-[(2,3-dihydroxypropyl)(3-hydroxypropyl)amino]ethyl]-oleamide

N -[3-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]propyl]-oleamide

N -[2-[(2,3-dihydroxypropyl)(3-decyloxypropyl)amino]ethyl]-isostearamide

N -[3-[(2,3-dihydroxypropyl)(2-decyloxyethyl)amino]propyl]-isostearamide

N -[2-[(2,3-dihydroxypropyl)(3-hydroxypropyl)amino]ethyl]-isostearamide

N -[3-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]propyl]-isostearamide

DETAILED DESCRIPTION OF THE INVENTION

The following three-step procedure is a general, representative example of the preparation of the class of compounds described in the present invention: 664 mmol of oleic acid is added to a 3-neck flask equipped with a temperature probe, a mechanical stirrer and a distillation trap (Dean-Stark trap) equipped with a reflux condenser. 664 mmol of 2-aminoethylethanolamine is added to the flask and the reaction is carried out under nitrogen atmosphere. The reaction mixture is heated to 150ºC, and the resulting water is collected in a distillation trap. After heating for approximately 6 hours, the reaction mixture is cooled and the resulting amide product is used directly in the next step without purification.

271 mmol of the product from the previous step is placed in a 3-neck flask equipped with a temperature probe and a mechanical stirrer. 275 ml of ethanol is added to the flask and a reflux condenser is connected. A solution consisting of 258 mmol glycidol in 70 ml ethanol is prepared and transferred to a dropping funnel with a nitrogen inlet on top of a reflux condenser. The reaction is carried out under a nitrogen atmosphere and the reaction mixture is heated to reflux (at approximately 80ºC). The glycidol solution is added dropwise to the flask over 30 minutes. After addition is complete, the reaction mixture is refluxed for an additional 6 hours. The reaction mixture is concentrated using a rotary evaporator until all ethanol is removed to form the 2,3-dihydroxypropyl adduct.

The product from the previous step is added to a 3-neck flask equipped with a temperature probe and a mechanical stirrer. Water is added and the reaction is carried out under nitrogen atmosphere and heated to 100°C. Molybdenum trioxide is added and the reaction mixture is heated until all the molybdenum has been absorbed. A small amount of antifoam is added and the reaction mixture is heated to 135°C under vacuum to remove water. The process oil is then added to the reaction mixture, which is lightly stirred before hot filtration through a pad of diatomaceous earth to form the final organomolybdenum product.

A wide variety of starting materials can be used in carrying out the above reactions, as depicted in General Reaction Scheme I. The first step uses a carbonyl-containing component, such as a carboxylic acid, a carboxylic acid ester, or a triglyceride. For carboxylic acids, the group R ¹ consisting of carbon atoms from 1 to 21 may be a linear, cyclic or branched saturated hydrocarbon group, or an unsaturated and/or polyunsaturated hydrocarbon group, or mixtures thereof. For esters of carboxylic acids, the group R ¹ consisting of carbon atoms from 1 to 21 may be a linear, cyclic or branched saturated hydrocarbon group, or an unsaturated and/or polyunsaturated hydrocarbon group, or mixtures thereof. For triglycerides, the R ¹ group, consisting of carbon atoms 1 to 21, may be a linear, cyclic or branched saturated hydrocarbon group, or an unsaturated and/or polyunsaturated hydrocarbon group, or mixtures thereof. For the reaction of a carboxylic acid or carboxylic acid ester with a primary amine compound, the stoichiometric reaction ratio is typically 1.0 mole of carboxylic acid or carboxylic acid ester to 1.0 mole of primary amine compound to produce the desired secondary amide. Slight excesses of the carboxylic acid or carboxylic acid ester or primary amine compound may be used, but this is generally neither necessary nor preferred. Preferred carboxylic acid esters are fatty acid methyl esters (FAME) and fatty acid ethyl esters, also called biodiesel. Biodiesel sources are the fatty oils described below. For the reaction of a triglyceride with a primary amine compound, the stoichiometric reaction ratio may be varied such that 1.0 moles of the triglyceride reacts with 1.0 to 3.0 moles of the primary amine compound to form the desired secondary amide and/or a mixture of the desired secondary amide with the corresponding mono- and dialkylglycerates. The carbon chains in the above examples of carbonyl-containing compounds may be formed from fatty oils such as coconut oil, hydrogenated coconut oil, fish oil, hydrogenated fish oil, tall oil, hydrogenated tall oil, corn oil, canola oil, cottonseed oil, olive oil , palm oil, peanut oil, safflower oil, sesame oil, sunflower oil, canola oil, or soybean oil. For a mixed primary/secondary amine compound, the R2 ¹ group may represent a hydrogen atom or a linear, cyclic or branched hydrocarbon chain containing from 1 to 20 carbon atoms, or mixtures thereof, and the number of methylene spacer groups ( n and m ) may vary in each case regardless of 1 to 5. In the final step, the molybdenum source may be molybdenum trioxide, molybdic acid, or a molybdate salt (eg, ammonium molybdate, ammonium heptamolybdate tetrahydrate, or sodium molybdate). Preferably, the molybdenum source is molybdenum trioxide.

The following examples were obtained using the typical methodology above:

Example 1 (Ex. 1)

The procedure for preparing the organic ligand, N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]-ethyl]-oleamide, was identical to the first two steps of a typical procedure. In the final step, 79 mmol of organic ligand was reacted with 54 mmol of water and 9 mmol of molybdenum trioxide as described in a typical procedure. Process oil (3.1 g) was added to form an organomolybdenum product containing 2.2% molybdenum.

Example 2 (Ex. 2)

The procedure for preparing the organic ligand, N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]-ethyl]-oleamide, was identical to the first two steps of a typical procedure. In the final step, 79 mmol of organic ligand was reacted at 105°C with 27 mmol of water and 18 mmol of molybdenum trioxide as described in a typical procedure. Process oil (3.1 g) was added to form an organomolybdenum product containing 4.2% molybdenum.

Example 3 (Ex. 3)

The procedure for preparing the organic ligand, N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]-ethyl]-oleamide, was identical to the first two steps of a typical procedure. In the final step, 79 mmol of organic ligand was reacted at 105°C with 27 mmol of water and 27 mmol of molybdenum trioxide as described in a typical procedure. Process oil (3.1 g) was added to form an organomolybdenum product containing 6.1% molybdenum.

Example 4 (Ex. 4)

The procedure for preparing the organic ligand, N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]-ethyl]-oleamide, was identical to the first two steps of a typical procedure. In the final step, 79 mmol of organic ligand was reacted at 110°C with 13 mmol of water and 36 mmol of molybdenum trioxide as described in a typical procedure. Example Product Ex. 5 was not filtered through a layer of diatomaceous earth. Process oil (3.1 g) was added to form an organomolybdenum product containing 8.2% molybdenum. This material was an extremely viscous, resinous material and was not evaluated in subsequent performance studies.

Example 5 (Ex. 5)

The procedure for preparing the organic ligand, N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]-ethyl]-oleamide, was identical to the first two steps of a typical procedure. In the final step, 68 mmol of organic ligand was reacted at 110°C with 12 mmol of water and 39 mmol of molybdenum trioxide as described in a typical procedure. Example Product Ex. 6 was not filtered through a layer of diatomaceous earth. Process oil (2.6 g) was added to form an unfiltered organomolybdenum product containing 9.8% molybdenum. This material was an extremely viscous, resinous material and was not evaluated in subsequent performance studies.

Example 6 (Ex. 6)

The procedure for preparing the organic ligand, N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-oleamide, was identical to the first two steps of a typical procedure, except that isotridecyloxypropyl-oleamide was used instead of 2-aminoethylethanolamine. 1,3-diaminopropane. In the final step, 52 mmol of organic ligand was reacted with 54 mmol of water and 9 mmol of molybdenum trioxide as described in a typical procedure. Process oil (3.1 g) was added to form an organomolybdenum product containing 2.0% molybdenum.

Example 7 (Ex. 7)

The procedure for preparing the organic ligand, N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-cocoamide, was identical to the first two steps of the typical procedure, except that methyl esters were used instead of oleic acid coconut oil, and methanol was collected in a distillation trap. In the final step, 94 mmol of organic ligand was reacted with 54 mmol of water and 9 mmol of molybdenum trioxide as described in a typical procedure. Process oil (3.1 g) was added to form an organomolybdenum product containing 2.2% molybdenum.

Example 8 (Ex. 8)

The procedure for preparing the organic ligand, N -[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]-cocoamide, was identical to the first two steps of the typical procedure, except that methyl esters were used instead of oleic acid coconut oil, isotridecyloxypropyl-1,3-diaminopropane was used instead of 2-aminoethylethanolamine, and the methanol was collected in a distillation trap. In the final step, 59 mmol of organic ligand was reacted with 54 mmol of water and 9 mmol of molybdenum trioxide as described in a typical procedure. Process oil (3.1 g) was added to form an organomolybdenum product containing 2.2% molybdenum.

Example 9 (Ex. 9)

The procedure for preparing the organic ligand, N -[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-isostearamide, was identical to the first two steps of a typical procedure, except that isostearic acid was used instead of oleic acid. In the final step, 76 mmol of organic ligand was reacted at 105° C. with 27 mmol of water and 27 mmol of molybdenum trioxide as described in a typical procedure. Process oil (3.1 g) was added to form an unfiltered organomolybdenum product containing 6.3% molybdenum.

The following compounds are included in the invention disclosed herein as comparative examples:

Comparative Example 1 (CEx. 1)

Glycerol monooleate (HiTEC® 7133 from Afton Chemical)

Comparative Example 2 (CEx. 2)

A comparative organomolybdenum compound containing 2.3% molybdenum was prepared as described in US4889647.

Individual compounds from the inventive class of molecules can be used as lubricating oil additives to reduce friction and/or provide additional wear protection at a dosage of 0.01 to 5.00 wt.% additive as part of the overall lubricant composition, preferably about 0 .08-3.00%, more preferably about 0.08-2.00%, even more preferably about 0.10-1.00%; or from about 50 ^ppm to 5000 ^ppm , preferably about 50-1000 ^ppm , and more preferably about 60-900 ^ppm , based on the amount of molybdenum in the lubricant additive. Additionally, these compounds may be used in combination with other additives such as dispersants, detergents, viscosity modifiers, antioxidants, other friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, fatty acid salts (soaps), and extreme pressure additives.

Dispersants that can be used include polyisobutylene disuccinimide dispersants, polypropylene monosuccinimide dispersants, polypropylene disuccinimide dispersants, ethylene monosuccinimide/propylene copolymer dispersants, ethylene dissuccinimide dispersants /propylene copolymer, Mannich dispersants, dispersant-antioxidant-olefin copolymers, low molecular weight ethylene/propylene succinimide dispersants, carboxyl dispersants, amine dispersants, borated dispersants, and molybdenum-containing dispersants.

Detergents that can be used include calcium sulfonate neutral detergents, magnesium sulfonate neutral detergents, high alkaline calcium sulfonate detergents, high alkaline magnesium sulfonate detergents, neutral calcium phenate detergents, neutral magnesium phenate detergents , high alkaline calcium phenate detergents, high alkaline magnesium phenate detergents, neutral calcium salicylate detergents, neutral magnesium salicylate detergents, high alkaline calcium salicylate detergents, high alkaline magnesium salicylate detergents, sodium sulfonate detergents, and detergents based on lithium sulfonate.

Any type of polymer viscosity index modifier can be used. Examples include olefin copolymers (OCPs), polyalkyl methacrylates (PAMAs), polyisobutylenes (PIBs), styrene block copolymers (such as styrene-isoprene copolymers, styrene-butadiene copolymers), and ethylene-alpha-olefin copolymers.

Additional molybdenum-based friction modifiers may be used to complement or enhance the overall effectiveness of the class of compounds of the present invention. Examples of the types of alternative friction modifiers that may be used include mononuclear molybdenum dithiocarbamates, dinuclear molybdenum dithiocarbamates, trinuclear molybdenum dithiocarbamates, sulfonated oxymolybdenedithiocarbamates containing sulfur and molybdenum compounds, molybdenum phosphorodithioates, sulfonated oxymolybdenedithiophosphates, thiomolybdate s tetraalkylammonium, molybdenum xanthates, molybdenum thioxanthates, oxythiomolybdate salts -imidazolium, and quaternary salts of ammonium oxythiomolybdate. Typical dosages of molybdenum-based friction modifiers vary from 50 ^ppm to 800 ^ppm molybdenum added to the final lubricant composition.

It is preferable that additives such as glycerol monooleate and organic friction modifiers derived from fatty oils and diethanolamine are not present as these types of organic friction modifiers will be demonstrated to be highly corrosive to copper and lead as determined by high temperature bench testing. corrosion (HTCBT, ASTM D6594 standard).

Preferred antiwear additives that may be used include primary and/or secondary zinc dialkyl dithiophosphate (ZDDP), triphenyl phosphorothioates, dialkyl phosphoric acid amine salts, monoalkyl phosphoric acid amine salts, dialkyl dithiophosphate succinates, dithiophosphoric carboxylic acid esters, trialkyl borate esters, borate derivatives fatty acid esters, and methylene bis(dibutyl dithiocarbamates).

Preferred antioxidants that may be used include dinonyldiphenylamine, monononyldiphenylamine, dioctyldiphenylamine, monooctyldiphenylamine, butyloctyldiphenylamine, monobutyldiphenylamine, dibutyldiphenylamine, nonylated phenyl-alpha-naphthylamine, octylated phenyl-alpha-naphthylamine, dodecylated phenyl-alpha-naphthylamine, 2. 6-di- tert-butylphenol, butylated hydroxytoluene, 4,4-methylenebis(2,6-di-tert-butylphenol), octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate, isotridecyl-3-[ 3,5-di-tert-butyl-4-hydroxyphenyl]propionate, 2-ethylhexyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate, isooctyl-3-[3,5-di- tert-butyl-4-hydroxyphenyl]propionate, and thiodiethylene bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl]propionate].

Preferred corrosion and rust inhibitors that may be used include ethoxylated phenols, alkenyl succinic acids, polyalkylene glycols, benzotriazole derivatives, tolutriazole derivatives, triazole derivatives, dimercaptothiadiazole derivatives, fatty acid and 4,5-dihydro-1H-imidazole derivatives, neutral calcium dinonyl naphthalene sulfonates , neutral zinc dinonylnaphthalene sulfonates, and neutral alkaline earth metal sulfonates.

Preferred extreme pressure additives that may be used include sulfonated isobutylene, sulfonated alpha-olefins, aliphatic amine phosphates, aromatic amine phosphates, dimercaptothiadiazole derivatives, zinc dialkyldithiocarbamates, dialkylammonium dialkyldithiocarbamates, and antimony dialkyldithiocarbamates.

Dosage levels for all of the above additives can vary significantly depending on the application, the solubility of the additive, the type of base fluid, and the final fluid performance requirements. Typical dosage levels typically range from 0.05 wt.% to 10.00 wt.%, based on the type of final lubricant processed. Base fluids may include petroleum-based or synthetic process materials that are included in the American Petroleum Institute (API) base stock classifications as Group I, Group II, Group III, Group IV, and Group V. Synthetic fluids include poly-alpha -olefins, polyols, esters, bio-based lubricants, and any combination thereof. The lubricating base oil or fluid is present in an amount of at least 80% of the total lubricating composition.

Examples of the types of finished lubricants that can be produced using the additives of the present invention include gasoline engine oils, heavy duty diesel engine oils, natural gas engine oils, medium speed diesel engine oils (high-speed or marine), SUV motor oils, two-stroke and four-stroke motorcycle motor oils, hybrid vehicle motor oils, tractor oils, racing oils, hydraulic fluids, automatic and manual transmission fluids, industrial and timing gear oils, and greases.

The performance evaluation results of the inventive examples and comparative examples are described in Examples 10-13. In Examples 10-12, the inventive and comparative materials were blended into SAE 0W-20 (0W-20 PCMO) passenger car engine oil at the dosages shown in Tables 1-6. This oil was fully formed, except that it did not contain any organic or organometallic friction modifier (FM). In Example 13, the products of the inventive and comparative examples were blended into commercial CK-4 equivalent SAE 15W-40 heavy duty diesel engine oil (15W-40 HDDEO) at the dosages shown in Table 7.

Example 10

Tribological Performance Testing with SRV

To collect the performance data shown in Table 1, the test method described in ASTM D5707 (Standard Test Method for Measuring Friction and Wear Properties of Lubricating Grease Using a High-Frequency, Linear-Oscillation (SRV) Test Machine) was followed. testing using a high-frequency, linear vibration (SRV) testing machine"). The results clearly show that all inventive examples provide improved wear protection and frictional performance compared to the reference 0W-20 PCMO oil, which does not contain an organic or organometallic friction modifier. In addition, all four examples of the invention match or exceed the friction performance of the CEx example. 1, a traditional organic friction modifier, while providing better wear protection, as evidenced by wear rates being between 9-27% lower for the inventive examples compared to CEx. 1. In addition, both examples corresponding to the invention Ex. 1 and Ex. 7 provide lower friction than the average CEx. 2, at dosages that introduce the same amount of molybdenum.

Table 1: Tribological performance test with SRV (ASTM D5707 standard)

Additive Dosage (wt.%) Mo in oil (ppm ^-1 ) Wear volume (µm) ³ ) Average friction coefficient 0W-20 PCMO 0 0 54055 0.144 +CEx. 1 0.80 0 41699 0.132 +CEx. 2 0.78 180 28845 0.127 +Ex. 1 0.82 180 38141 0.122 +Ex. 6 0.90 180 3147 0.133 +Ex. 7 0.82 180 30163 0.116 +Ex. 8 0.82 180 31351 0.131

Example 11

Testing tribological characteristics on a four-ball friction machine

To collect the performance data shown in Table 2, the test method described in ASTM D4172 B (Standard Test Method for Wear Preventive Characteristics of Lubricating Fluid (Four-Ball Method)) was followed. four-ball method)")). Based on the four-ball test results, the four inventive examples show a favorable reduction in average coefficient of friction compared to the reference 0W-20 PCMO oil that does not contain a friction modifier. In addition, all examples of the invention match or significantly improve wear protection compared to the reference 0W-20 PCMO oil, as indicated by wear scar diameters. According to this test method according to the invention Ex. 8 provides friction and wear characteristics equivalent to both comparative examples.

Table 2: Tribological testing on a 4-ball friction machine (ASTM D4172 B standard)

Additive Dosage (wt.%) Mo in oil (ppm ^-1 ) Wear scar diameter (mm) Average friction coefficient 0W-20 PCMO 0 0 0.45 0.099 +CEx. 1 0.80 0 0.34 0.062 +CEx. 2 0.78 180 0.35 0.066 +Ex. 1 0.82 180 0.43 0.075 +Ex. 6 0.90 180 0.34 0.075 +Ex. 7 0.82 180 0.45 0.083 +Ex. 8 0.82 180 0.35 0.063

Example 12

Testing tribological characteristics on a mini-traction machine

A mini-traction machine (MTM) was used to evaluate the frictional performance of lubricants under boundary and mixed lubrication conditions (Stribeck curve) using a ball-on-disc configuration. The MTM consists of a rotating 52100 steel ball pressed against an independently rotating 52100 steel disc immersed in a lubricant. Operating conditions are adjusted by independently adjusting the rotation speeds of the shafts that drive the ball and disc to obtain a specific combination of rolling and sliding speeds for the rolling-sliding relationship, as well as adjusting the contact force and oil bath temperature. The test method parameters used to collect the friction performance data shown in Tables 3-6 from a mini traction machine (MTM) are as follows: load 35 N (~1 GPa), 50% slip:roll ratio, running speed from 3000 mm/s to 10 mm/s, steel grade 52100. For each composition, three Stribeck curves were plotted at 40°C, 60°C, 80°C, 100°C, 120°C, and 140°C. For each temperature, the average of three runs was recorded.

The data in Table 3 refers to the friction coefficients for each oil in the boundary lubrication mode. All four examples of the invention are reported to provide improved boundary lubrication at or near temperatures of 100° C. compared to the reference 0W-20 PCMO oil containing no organic or organometallic friction modifiers. In particular, example Ex. 1 according to the invention provides improved boundary lubrication at temperatures below 80ºC. In addition, it both matches and slightly improves the friction performance of the comparative examples at temperatures of 100ºC or higher. Table 4 contains the results for the Stribeck coefficients obtained for oils at each temperature. At temperatures of 100°C or higher, all examples according to the invention significantly improved the friction characteristics of the oil, compared with the reference oil 0W-20 PCMO. Similar to the friction characteristics data in the boundary lubrication mode, the oil containing the inventive example Ex. 1 exhibits significantly lower Stribeck coefficients than every other friction modifier additive, as assessed at temperatures between 100-140°C, and its performance is second only to the CEx example. 2 at 80°C. These results indicate that the Ex. 1 according to the invention improves frictional characteristics not only in the boundary lubrication mode, but also in mixed or elastohydrodynamic modes.

Table 3: Tribological performance test on MTM

Limit friction coefficient* at a given temperature Additive Dosage (wt.%) Mo in oil (ppm ^-1 ) 40°C 60°C 80°C 100°C 120°C 140°C 0W-20 PCMO 0 0 0.076 0.094 0.113 0.128 0.127 0.128 +CEx. 1 0.80 0 0.091 0.095 0.090 0.090 0.088 0.077 +CEx. 2 0.78 180 0.084 0.098 0.097 0.092 0.086 0.086 +Ex. 1 0.82 180 0.093 0.102 0.100 0.091 0.085 0.082 +Ex. 6 0.90 180 0.101 0.108 0.105 0.100 0.096 0.089 +Ex. 7 0.82 180 0.083 0.114 0.114 0.106 0.098 0.088 +Ex. 8 0.82 180 0.108 0.119 0.114 0.105 0.098 0.091

*Reported coefficients represent the average of three experiments. The limit coefficient is the coefficient of friction at a speed of 10 mm/sec.

Table 4: Tribological performance test on MTM

Stribeck coefficient* at a given temperature Additive Dosage (wt.%) Mo in oil (ppm ^-1 ) 40°C 60°C 80°C 100°C 120°C 140°C 0W-20 PCMO 0 0 0.135 0.141 0.167 0.219 0.268 0.278 +CEx. 1 0.80 0 0.142 0.156 0.168 0.180 0.191 0.181 +CEx. 2 0.78 180 0.135 0.142 0.157 0.172 0.183 0.190 +Ex. 1 0.82 180 0.150 0.152 0.161 0.160 0.167 0.174 +Ex. 6 0.90 180 0.155 0.162 0.174 0.186 0.200 0.208 +Ex. 7 0.82 180 0.134 0.158 0.173 0.183 0.186 0.184 +Ex. 8 0.82 180 0.163 0.173 0.188 0.198 0.206 0.208

*Stribeck coefficients are calculated using the integration of the Stribeck curve at each individual temperature.

The data in Table 5 refers to the friction coefficients in the boundary lubrication mode for oils containing Ex as an example. 3 and example Ex. 9 according to the invention. For this study, additive dosages were varied to add between 60 and 900 ^ppm molybdenum to the final fluid. Both inventive examples are reported to provide improved boundary lubrication at temperatures of 80° C. or higher compared to the reference 0W-20 PCMO oil containing no organic or organometallic friction modifiers. Small improvements in the coefficient of boundary friction were observed for both examples according to the invention even at the lowest dosage (60 ^ppm Mo). Significant reductions in boundary friction were obtained when molybdenum dosage was between 200-600 ^ppm . Compositions containing the Ex. 3 demonstrated exceptional improvements in performance, especially at the highest temperatures and dosages. For example, compositions containing 750-900 ^ppm molybdenum had boundary friction coefficients 50% lower than those of the reference oil without any friction modifier, at an operating temperature of 140°C. Table 6 shows the results of the Stribeck coefficients obtained for oils at each temperature and dosage. Again, the data shows that compositions containing any of the inventive examples, at all dosages, provide lower friction at temperatures of 80°C or higher, compared to the 0W-20 PCMO reference oil containing no friction modifier. In particular, the example according to the invention is Ex. 3 consistently showed lower Stribeck coefficients at all dosages when the temperature was 60°C or higher. With regard to boundary friction coefficients, significant improvements in friction, as evidenced by lower Stribeck coefficients, were shown for compositions containing at least 450 ^ppm molybdenum (total dosage 0.74 wt.%). In addition, this total dosage is approximately equivalent to that used for the comparative organic friction modifier, example CEx. 1 (see results for CEx. 1 at 0.80 wt.% in Table 4). Both compositions containing 450 ^ppm Mo from any of Ex. 3 or Ex. 9 are consistently superior to the CEx example. 1 at any estimated operating temperature. Additionally, additional improvements were observed when the dosage of molybdenum was increased. In particular, at 120-140°C, the Stribeck coefficient for a composition containing 750 ^ppm Mo from example Ex. 3 according to the invention was approximately 55% lower than that of a reference oil containing neither an organic nor an organometallic friction modifier. The data in Tables 5 and 6 again show that the examples of the invention are effective friction modifiers over a wide range of dosages and temperatures, and in both boundary and mixed lubrication modes.

Table 5: Tribological performance test on MTM at various dosages

Boundary friction coefficient* at a given temperature Additive Dosage (wt.%) Mo in oil (ppm ^-1 ) 40°C 60°C 80°C 100°C 120°C 140°C 0W-20 PCMO 0 0 0.076 0.094 0.113 0.128 0.127 0.128 +Ex. 3 0.10 60 0.072 0.090 0.103 0.107 0.108 0.112 +Ex. 3 0.33 200 0.072 0.089 0.097 0.100 0.093 0.094 +Ex. 3 0.74 450 0.088 0.096 0.097 0.096 0.089 0.085 +Ex. 3 0.98 600 0.098 0.100 0.098 0.091 0.077 0.072 +Ex. 3 1.23 750 0.087 0.096 0.098 0.090 0.078 0.069 +Ex. 3 1.48 900 0.092 0.105 0.098 0.088 0.075 0.063 +Ex. 9 0.10 60 0.086 0.106 0.111 0.111 0.112 0.114 +Ex. 9 0.32 200 0.086 0.100 0.103 0.100 0.096 0.104 +Ex. 9 0.71 450 0.079 0.087 0.093 0.092 0.088 0.081 +Ex. 9 0.95 600 0.090 0.105 0.106 0.099 0.092 0.085 +Ex. 9 1.19 750 0.098 0.106 0.105 0.099 0.092 0.084 +Ex. 9 1.43 900 0.084 0.094 0.100 0.096 0.090 0.083

*Reported Stribeck coefficients represent the average of three experiments. The limit coefficient is the coefficient of friction at a speed of 10 mm/sec.

Table 6: Tribological performance testing on MTM at various dosages

Stribeck coefficient* at a given temperature Additive Dosage (wt.%) Mo in oil (ppm ^-1 ) 40°C 60°C 80°C 100°C 120°C 140°C 0W-20 PCMO 0 0 0.135 0.141 0.167 0.219 0.268 0.278 +Ex. 3 0.10 60 0.127 0.134 0.153 0.176 0.218 0.257 +Ex. 3 0.33 200 0.129 0.135 0.150 0.170 0.187 0.216 +Ex. 3 0.74 450 0.135 0.136 0.137 0.143 0.148 0.154 +Ex. 3 0.98 600 0.142 0.141 0.140 0.136 0.129 0.126 +Ex. 3 1.23 750 0.134 0.132 0.132 0.127 0.121 0.119 +Ex. 3 1.48 900 0.140 0.147 0.147 0.142 0.136 0.127 +Ex. 9 0.10 60 0.137 0.150 0.170 0.200 0.239 0.260 +Ex. 9 0.32 200 0.139 0.144 0.155 0.169 0.191 0.232 +Ex. 9 0.71 450 0.131 0.128 0.132 0.137 0.146 0.152 +Ex. 9 0.95 600 0.140 0.142 0.146 0.148 0.149 0.158 +Ex. 9 1.19 750 0.149 0.152 0.156 0.168 0.176 0.175 +Ex. 9 1.43 900 0.134 0.133 0.138 0.142 0.144 0.144

*Stribeck coefficients are calculated using the integration of the Stribeck curve at each individual temperature.

Example 13

Corrosion testing of copper and lead by High Temperature Corrosion Bench Test (HTCBT).

To collect the copper and lead corrosion data shown in Table 7, the test method described for ASTM D6594 (Standard Test Method for Evaluation of Corrosiveness of Diesel Engine Oil at 135 °C) was followed. engine at 135ºС")). For API CK-4 and equivalent oils, the limits for passing the HTCBT test are a maximum of 20 ^ppm for copper, a maximum of 120 ^ppm for lead, and a maximum of 3 copper ratings. According to the data presented in Table 7, it is clear that the introduction of the CEx. 1 as an organic friction modifier in 15W-40 resulted in significant corrosion of both copper and lead in the HDDEO test. Composition containing CEx. 1, which is an ester-based additive only, has no effect on copper corrosion, and has no effect on lead corrosion at all. Alternatively, CEx. 2 is an organomolybdenum additive with an organic component including a mixture of both amide-based and ester-based compounds. For For CEx. 2 The oil now passes the copper corrosion test at a low dosage of molybdenum. At higher dosages, CEx.2 provides an overall additive potency equivalent to the CEx example. 1. While CEx. 2 is still not effective at all against corrosion of both copper and lead, the observed values for lead were reduced by more than 60%. Examples according to the invention are organomolybdenum additives with an organic component including amide-based ligands only. When the inventive example Ex. 1 is compared with CEx. 2, Ex. 1 exhibits significant reductions in corrosion of both copper and lead. Example Ex. 1 passes the HTCBT test for copper at both low and high dosages, and passes the test for lead at lower dosages. For both dosages, Example Ex. according to the invention. 1 represents an approximately 67% reduction in lead corrosion compared to the CEx example. 2. Corresponding to the invention Ex. 2 represents a twofold increase in the molybdenum content in the additive compared to Ex. 1. HTCBT test results for Ex. 2 shows the test pass values for copper and lead at both dosages. These improvements were even more pronounced for the Ex example. 3 according to the invention, which represents a threefold increase in molybdenum content compared to example Ex. 1. Again, the HTCBT test results show a significant reduction in both copper and lead corrosion values. At a higher dosage of molybdenum, the results for lead from example Ex. 3 are more than 90% lower than for CEx. 2, and more than 96% lower than for CEx. 1. Finally, according to the invention, example Ex. 9 represents an organomolybdenum compound containing a fully saturated amide-based organic ligand. HTCBT test results for Ex. 9 show that this additive does not contribute to all copper corrosion, as confirmed by the copper equivalent values and evaluation compared to the reference oil. In addition, compositions containing Ex. 9 show only very moderate increases in lead values at both dosages. The results show that Ex. 9, and to a lesser extent Ex. 2 and 3 can be used at higher dosages to introduce more molybdenum if friction or wear characteristics are desired.

Table 7: HTCBT Copper and Lead Corrosion Test (ASTM D6594)

Additive Dosage (wt.%) Mo in oil (ppm ^-1 ) Cu
(million ^-1 )* Grade
Cu* Pb
(million ^-1 )* 15W-40 HDDEO 0 0 6.0 1b 7.5 +CEx. 1 0.75 0 40.0 2e 925.0 +CEx. 2 0.43 100 15.5 1b/2c 196.0 0.87 200 104.0 2c 365.5 +Ex. 1 0.45 100 8.0 1b 63.0 0.91 200 12.0 1b 125.5 +Ex. 2 0.24 100 7.5 1b 42.0 0.49 200 10.5 1b 85.0 +Ex. 3 0.16 100 13.5 2e 23.5 0.33 200 6.0 1b 33.5 +Ex. 9 0.16 100 5.5 1b 18.0 0.32 200 6.5 1b 33.0

*Values for copper and lead are the average of at least two tests. If experiments carried out twice give different estimates for copper, both estimates are given.

Friction, wear and corrosion performance testing results demonstrate that the inventive examples represent a new class of additives capable of matching or exceeding the friction and wear performance of traditional additives while significantly reducing the severity of observed copper and lead corrosion.

Claims (52)

1. Molybdate ester represented by the following formula: where R ¹ represents a hydrocarbon chain containing from 11 to 21 carbon atoms, R ² represents either a hydrogen atom or a hydrocarbon chain containing from 1 to 20 carbon atoms, and m and n are independently from 1 to 5. 2. Molybdate ester according to claim 1, formed from one of the following compounds: N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]alkanamide; N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]isostearamide; N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-cocoamide; N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]oleamide; N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]alkanamide; N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]isostearamide; N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]-cocoamide; And N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]-oleamide. 3. A compound used as a lubricating oil additive and produced by the reaction (a) a carboxylic acid containing from 12 to 22 carbon atoms, or a methyl ester of a carboxylic acid which contains from 12 to 22 carbon atoms, or an ethyl ester of a carboxylic acid which contains from 12 to 22 carbon atoms, with (b) one of (i) 2-aminoethylethanolamine, (ii) alkyloxypropyl-1,3-diaminopropane, (iii) alkyloxyethyl-1,3-diaminopropane, and (iv) alkyloxypropyl-1,2-diaminoethane; And (c) glycidol; (d) followed by reaction with a source of molybdenum. 4. A lubricating composition comprising a major amount of a lubricating base fluid and a molybdate ester represented by the following formula: where R ¹ represents a hydrocarbon chain containing from 11 to 21 carbon atoms, R ² represents either a hydrogen atom or a hydrocarbon chain containing from 1 to 20 carbon atoms, and m and n are independently from 1 to 5, and a molybdate ester is present in an amount sufficient to create a concentration of about 50-5000 ^ppm molybdenum in the lubricant composition. 5. The lubricant composition according to claim 4, in which the molybdate ester is present in an amount sufficient to create a concentration of about 50-1000 ^ppm molybdenum. 6. A lubricating composition comprising a major amount of a lubricating base fluid and a compound produced by the reaction (a) a carboxylic acid containing from 12 to 22 carbon atoms, or a methyl ester of a carboxylic acid which contains from 12 to 22 carbon atoms, or an ethyl ester of a carboxylic acid which contains from 12 to 22 carbon atoms, with (b) one of (i) 2-aminoethylethanolamine, (ii) alkyloxypropyl-1,3-diaminopropane, (iii) alkyloxyethyl-1,3-diaminopropane, and (iv) alkyloxypropyl-1,2-diaminoethane; And (c) glycidol; (d) followed by reaction with a source of molybdenum. 7. The lubricant composition according to claim 4, where the molybdate ester is formed from one of the following compounds: N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]alkanamide; N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]isostearamide; N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-cocoamide; N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]oleamide; N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]alkanamide; N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]isostearamide; N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]-cocoamide; And N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]-oleamide. 8. Method for producing molybdate ester, including reaction steps (a) a carboxylic acid or ester, with (b) one of (i) 2-aminoethylethanolamine, (ii) alkyloxypropyl-1,3-diaminopropane, (iii) alkyloxyethyl-1,3-diaminopropane, and (iv) alkyloxypropyl-1,2-diaminoethane; And (c) glycidol; (d) followed by reaction with a source of molybdenum, where the molybdate ester is represented by the following formula: where R ¹ represents a hydrocarbon chain containing from 11 to 21 carbon atoms, R ² represents either a hydrogen atom or a hydrocarbon chain containing from 1 to 20 carbon atoms, and m and n are independently from 1 to 5. 9. The method of claim 8, wherein the molybdate ester is formed from one of the following compounds: N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]alkanamide; N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]isostearamide; N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]-cocoamide; N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]oleamide; N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]alkanamide; N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]isostearamide; N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]-cocoamide; And N-[3-[(2,3-dihydroxypropyl)(3-alkyloxypropyl)amino]propyl]-oleamide.