阅读说明：本技术 作为润滑剂添加剂的低腐蚀性有机钼化合物 (Low corrosion organomolybdenum compounds as lubricant additives ) 是由 布莱恩·M·凯西 文森特·J·加托 于 2020-04-02 设计创作，主要内容包括：由下式表示的钼酸酯：其中R～(1)为烃链,R～(2)为氢原子或烃链,并且m和n独立地为1至5,当以足以提供约50ppm至5000ppm的钼的量用于润滑组合物中时,在摩擦和磨损减少方面是有效的,同时提供改善的抗铜和铅腐蚀的保护。(An molybdic acid ester represented by the formula: wherein R is 1 Is a hydrocarbon chain, R 2 Is a hydrogen atom or hydrocarbon chain, and m and n are independently 1 to 5, are effective in friction and wear reduction while providing improved protection against copper and lead corrosion when used in lubricating compositions in amounts sufficient to provide about 50 to 5000ppm molybdenum.)

1. An molybdic acid ester represented by the formula:

wherein R is¹Is a hydrocarbon chain, R²Is a hydrogen atom or a hydrocarbon chain, and m and n are independently 1 to 5.

2. The molybdic acid ester according to claim 1, derived 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 ] cocamide

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 ] cocamide

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

3. A compound prepared by reacting

(a) Carboxylic acids or esters, with

(b) One of (i) 2-aminoethyl-ethanolamine, (ii) alkyloxypropyl-1, 3-diaminopropane, (iii) alkyloxyethyl-1, 3-diaminopropane, and (iv) alkyloxypropyl-1, 2-diaminoethane; and

(c) glycidol is reacted;

(d) and then reacted with a molybdenum source.

4. A lubricating composition comprising a major amount of a lubricating base fluid and an ester molybdate represented by the formula:

wherein R is¹Is a hydrocarbon chain, R²Is a hydrogen atom or a hydrocarbon chain, and m and n are independently 1 to 5, said molybdate ester being present in an amount sufficient to provide about 50 to 5000ppm of molybdenum in the lubricating composition.

5. The lubricating composition of claim 4, wherein the molybdate ester is present in an amount sufficient to provide about 50 to 1000ppm molybdenum.

6. A lubricating composition comprising a major amount of a lubricating base fluid and a compound prepared by: by making

(a) Carboxylic acids or esters, with

(b) One of (i) 2-aminoethyl-ethanolamine, (ii) alkyloxypropyl-1, 3-diaminopropane, (iii) alkyloxyethyl-1, 3-diaminopropane, and (iv) alkyloxypropyl-1, 2-diaminoethane; and

(c) glycidol is reacted;

(d) and then reacted with a molybdenum source.

7. The lubricating composition of claim 4, wherein the molybdate ester is derived 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 ] cocamide

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 ] cocamide

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

8. A method of making a molybdate ester comprising the steps of: make it

(a) Carboxylic acids or esters, with

(b) One of (i) 2-aminoethyl-ethanolamine, (ii) alkyloxypropyl-1, 3-diaminopropane, (iii) alkyloxyethyl-1, 3-diaminopropane, and (iv) alkyloxypropyl-1, 2-diaminoethane; and

(c) glycidol is reacted;

(d) and then reacted with a molybdenum source.

9. The method of claim 8, wherein the molybdate ester is derived 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 ] cocamide

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 ] cocamide

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

Technical Field

The present invention includes the development of less corrosive, higher performance organomolybdenum compounds for use as additives in lubricants. Lubricants containing these compounds have demonstrated improved performance in terms of friction reduction, wear protection, and copper and lead corrosion, particularly for diesel and passenger car engine oil applications where high performance, more durable additives are required in terms of oxidation and hydrolytic stability.

One class of compounds of the present invention can be represented by the formula:

wherein R is¹Is a hydrocarbon chain, R²Is a hydrogen atom or a hydrocarbon chain. R¹The group consists of an unsaturated and/or saturated and/or branched hydrocarbon chain containing from 1 to 21 carbon atoms. Preferably R¹Is unsaturated or branched. Also preferred is R¹The groups are unsaturated and branched. Also preferred is R¹The group consists of a hydrocarbon chain containing 11 to 21 carbon atoms. R²The group may be a hydrogen atom or a linear, cyclic or branched hydrocarbon chain containing 1 to 20 carbon atoms. The number of methylene spacers (n and m) is each independently 1 to 5. Preferably the number of methylene spacers (n and m) is each independently 2 or 3.

Preferred organomolybdenum compounds are prepared from the reaction of 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 as lubricant additives in passenger car and heavy duty diesel engine oils used at treatment rates of 0.05 wt.% to 5.00 wt.%.

Discussion of the prior art

GB796732 describes the preparation of organomolybdenum compounds as reaction products of alpha-or beta-alkane diols with molybdenum sources and the use of these compounds as corrosion inhibitors and antioxidants in lubricating oil compositions derived primarily from mineral oils. One class of compounds of the present invention is chemically distinct and outside the class described in GB 796732. Furthermore, GB796732 does not consider the effect of the examples in improving friction performance and/or wear protection.

US20170044456 describes a lubricating composition which is less corrosive to copper and lead for heavy duty diesel formulations which allow the use of organomolybdenum. The lubricating composition discussed in US20170044456 is a formulated solution for copper and lead corrosion involving the pairing of a sulfur-free organomolybdenum, a sulfur-containing organomolybdenum, and a specific triazole-based corrosion inhibitor. The invention provided herein differs significantly in that the additives represented by the inventive examples are inherently less aggressive towards copper and lead than the comparative organic and/or organometallic additives.

Examples of ligands for the preparation of such compounds are contained in DE1061966 and JP 35012097. However, neither DE1061966 nor JP35012097 describe any subsequent reaction of these ligands with any metal, including molybdenum. Furthermore, the preparation of unsaturated or branched examples of N- [2- [ (2, 3-dihydroxy-propyl) (2-hydroxyethyl) amino ] ethyl ] -alkylamides is not discussed and does not belong to the class of organomolybdenum compounds based on the ligand N- [3- [ (2, 3-dihydroxypropyl) (3-alkoxypropyl) amino ] propyl ] -alkylamides of the present invention. Furthermore, neither DE1061966 nor JP35012097 consider the use, for example, of a class of compounds of the invention in lubricants as additives for friction modification or wear protection.

DE1061966 describes the preparation of 2, 3-dihydroxy compounds related to the ligands of the invention by reacting the intermediate alkylamides N- [2- [ (2-hydroxyethyl) amino ] ethyl ] -with alpha-chloroethanol or epichlorohydrin. The process may require the use of caustic and produce halogenated waste. In the invention provided herein, alternatively, the intermediate alkyl amide amine is reacted with glycidol in the presence of ethanol. These reactions benefit from complete atom economy and do not produce waste. The ethanol can be separated from the reaction by simple distillation and recycled to the process.

Background

Disclosure of Invention

Conventional organic friction modifiers such as glycerol monooleate are susceptible to oxidation and hydrolysis when used as additives in engine oil applications. Thus, these additives and their degradation products can lead to reduced performance and/or corrosion (i.e., copper and/or lead). The invention disclosed herein meets or exceeds the friction reduction of conventional additives while also providing significant improvements in copper and lead corrosion as determined by ASTM D6594, standard test method for evaluating diesel engine oil corrosion at 135 ℃ (HTCBT). Additionally, the organo-molybdenum compounds are multifunctional lubricant additives that provide improved oxidation, friction reduction and wear protection properties.

Based on the results of the tribological performance, wear protection and corrosion tests set forth below, the examples of the present invention have proven to represent a new class of additives that can meet or exceed the tribological and wear performance of conventional additives while significantly reducing the severity of copper and lead corrosion observed. Such compounds of the invention are particularly useful in passenger car engine oil and heavy duty diesel engine oil applications where high performance, more durable friction modifiers and/or antiwear additives are required in terms of oxidation and hydrolytic stability.

A class of compounds of the present invention can be prepared via the following general reaction scheme:

in a first step, a carbonyl-containing compound such as a carboxylic acid, carboxylic acid ester, or triglyceride is reacted with a mixed primary/secondary amine-containing compound to form a secondary amide. In a second step, the secondary amide intermediate is further reacted with glycidol to give the 2, 3-dihydroxypropyl adduct. The second step may be carried out in the presence of a protic solvent such as methanol or ethanol to improve the reaction efficiency. 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 may be diluted with a process oil to provide the final organomolybdenum product.

As highlighted above, such compounds in 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 organomolybdenum-containing product may be diluted with a process oil. The relative proportions of organic ligand, molybdenum source, and process oil can be varied such that the final organomolybdenum product contains 0.5 wt.% to 15.0 wt.% molybdenum. More preferably, the final organomolybdenum product contains from 2.0 wt% to 10.0 wt% molybdenum. The organic ligand can be described as the reaction product of a carboxylic acid or ester or triglyceride, a mixed primary/secondary amine-containing compound, and glycidol. Non-limiting examples of organic ligands useful in preparing 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 ] myristoleamide

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

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 ] palmitoleimide

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 ] palmitoleid amide

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 ] palmitoleid amide

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-decyloxypropyl) amino ] propyl ] palmitoleid amide

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

The following three-step procedure is a general representative example for the preparation of a class of compounds described in the present invention: 664mmol of oleic acid was added to a three-necked flask equipped with a temperature probe, a mechanical stirrer and a distillation trap equipped with a condenser. 664mmol of 2-aminoethyl-ethanolamine was added to the flask and the reaction was placed under a nitrogen atmosphere. The reaction was heated to 150 ℃ and the resulting water was collected in a distillation trap. After heating for about 6 hours, the reaction was cooled and the product amide was used in the next step without purification.

271mmol of the product from the previous step were added to a three-neck flask equipped with a temperature probe and a mechanical stirrer. 275mL of ethanol were added to the flask and a reflux condenser was attached. A solution consisting of 258mmol of glycidol in 70mL of ethanol was prepared and transferred to an addition funnel with a nitrogen inlet connected to the top of the reflux condenser. The reaction was placed under a nitrogen atmosphere and heated to reflux (about 80 ℃). The glycidol solution was added dropwise to the flask over 30 minutes. After the addition was complete, the reaction was refluxed for an additional 6 hours. The reaction was concentrated by rotary evaporation until all ethanol was removed to give the 2, 3-dihydroxypropyl adduct.

The product from the previous step was added to a three-neck flask equipped with a temperature probe and a mechanical stirrer. Water was added and the reaction was placed under a nitrogen atmosphere and heated to 100 ℃. Molybdenum trioxide was added and the reaction was heated until all the molybdenum was consumed. A small amount of defoamer was added and the reaction was heated to 135 ℃ under vacuum to remove water. The process oil was then added to the reaction mixture, which was briefly stirred, and then filtered hot through a pad of celite to give the final organomolybdenum product.

In carrying out the above reaction, various starting materials may be used, as described in general reaction scheme I. In the first step, compounds containing carbonyl groups, e.g. carboxylic acids, carboxylic acidsAcid esters or triglycerides. For carboxylic acids, R consisting of 1 to 21 carbon atoms¹The groups may be linear, cyclic or branched saturated hydrocarbons or unsaturated and/or polyunsaturated hydrocarbons or mixtures thereof. For carboxylic acid esters, R consisting of 1 to 21 carbon atoms¹The groups may be linear, cyclic or branched saturated hydrocarbons or unsaturated and/or polyunsaturated hydrocarbons or mixtures thereof. For triglycerides, R consisting of 1 to 21 carbon atoms¹The groups may be linear, cyclic or branched saturated hydrocarbons or unsaturated and/or polyunsaturated hydrocarbons or mixtures thereof. For the reaction of a carboxylic acid or carboxylic acid ester with a primary amine-containing compound, the reaction stoichiometry is typically 1.0 mole of carboxylic acid or carboxylic acid ester to 1.0 mole of primary amine-containing compound to form the desired secondary amide. A slight excess of carboxylic acid or ester, or primary amine-containing compound, may be used, but is generally not necessary, nor preferred. Preferred carboxylic acid esters are fatty acid methyl esters (FAME's) and fatty acid ethyl esters, also known as biodiesel. The source of biodiesel is the fatty oil described below. For the reaction of triglycerides with primary amine-containing compounds, the reaction stoichiometry can be varied such that 1.0 mole of triglyceride reacts with 1.0 to 3.0 moles of primary amine-containing compound to form the desired secondary amide and/or the desired mixture of secondary amide with the corresponding mono-and di-alkyl glycerolates. The carbon chain in the above examples of carbonyl-containing compounds may be derived from fatty oils such as coconut oil, hydrogenated coconut oil, fish oil, hydrogenated fish oil, tallow, hydrogenated tallow, corn oil, rapeseed oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, sunflower oil, canola oil, and soybean oil. For mixed primary/secondary amine-containing compounds, R²The groups may be hydrogen atoms or linear, cyclic or branched hydrocarbon chains containing from 1 to 20 carbon atoms or mixtures thereof, and the number of methylene spacer groups (n and m) may each independently vary from 1 to 5. In the final step, the molybdenum source may be molybdenum trioxide, molybdic acid or molybdate (e.g., ammonium molybdate, ammonium heptamolybdate tetrahydrate, or sodium molybdate). Preferably, the molybdenum source is molybdenum trioxide.

The following examples were prepared using the representative procedures provided above:

example 1(Ex.1)

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

Example 2(Ex.2)

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

Example 3(Ex.3)

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

Example 4(Ex.4)

The procedure for the preparation of the organic ligand N- [2- [ (2, 3-dihydroxypropyl) (2-hydroxyethyl) amino ] -ethyl ] oleamide was the same as the first two steps of the representative procedure. In the final step, 79mmol of organic ligand was reacted with 13mmol of water and 36mmol of molybdenum trioxide as described in the representative procedure at 110 ℃. Ex.5 was not filtered through a pad of celite. Process oil (3.1g) was added to produce an organomolybdenum product containing 8.2% molybdenum. This material was a very viscous, tar-like material and was not evaluated in subsequent performance studies.

Example 5(Ex.5)

The procedure for the preparation of the organic ligand N- [2- [ (2, 3-dihydroxypropyl) (2-hydroxyethyl) amino ] ethyl ] oleamide was the same as the first two steps of the representative procedure. In the final step, 68mmol of organic ligand was reacted with 12mmol of water and 39mmol of molybdenum trioxide as described in the representative procedure at 110 ℃. Ex.6 was not filtered through a pad of celite. Process oil (2.6g) was added to produce an unfiltered organomolybdenum product containing 9.8% molybdenum. This material was a very viscous, tar-like material and was not evaluated in subsequent performance studies.

Example 6(Ex.6)

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

Example 7(Ex.7)

The procedure for the preparation of the organic ligand N- [2- [ (2, 3-dihydroxypropyl) (2-hydroxyethyl) amino ] ethyl ] cocamide was the same as the first two steps of the representative procedure, but cocomethyl ester was used instead of oleic acid and methanol was collected in a distillation trap. In the final step, 94mmol of organic ligand was reacted with 54mmol of water and 9mmol of molybdenum trioxide as described in the representative procedure. Process oil (3.1g) was added to produce an organomolybdenum product containing 2.2% molybdenum.

Example 8(Ex.8)

The procedure for the preparation of the organic ligand N- [3- [ (2, 3-dihydroxypropyl) (3-isotridecyloxy-propyl) amino ] propyl ] cocamide was the same as the first two steps of the representative procedure, except that cocomethyl ester was used instead of oleic acid, isotridecyloxypropyl-1, 3-diaminopropane was used instead of 2-aminoethylethanolamine, and methanol was collected in a distillation trap. In the final step, 59mmol of organic ligand was reacted with 54mmol of water and 9mmol of molybdenum trioxide as described in the representative procedure. Process oil (3.1g) was added to produce an organomolybdenum product containing 2.2% molybdenum.

Example 9(Ex.9)

The procedure for the preparation of the organic ligand N- [2- [ (2, 3-dihydroxypropyl) (2-hydroxyethyl) -amino ] ethyl ] isostearamide was the same as the first two steps of the representative procedure, but using isostearic acid instead of oleic acid. In the final step, 76mmol of organic ligand was reacted with 27mmol of water and 27mmol of molybdenum trioxide as described in the representative procedure at 105 ℃. Process oil (3.1g) was added to produce an organomolybdenum product containing 6.3% molybdenum.

The following compounds were included as comparative examples of the invention disclosed herein:

COMPARATIVE EXAMPLE 1(CEx.1)

Glycerol monooleate (available from Afton Chemical)7133)

COMPARATIVE EXAMPLE 2(CEx.2)

A comparative organomolybdenum compound containing 2.3% molybdenum was prepared as described in US 4889647.

Individual compounds from the molecular classes of the present invention may be used as additives in lubricants for friction reduction and/or supplemental wear protection at a treat rate of from 0.01% to 5.00% by weight of the additives as part of the total lubricating composition, preferably from about 0.08% to 3.00%, more preferably from about 0.08% to 2.00%, still more preferably from about 0.10% to 1.00%; or about 50ppm to 5000ppm, preferably about 50ppm to 1000ppm, more preferably about 60ppm to 900ppm, based on the amount of molybdenum in the additive delivered to the lubricant. In addition, these compounds may be used in combination with other additives such as dispersants, detergents, viscosity modifiers, antioxidants, other friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, salts of fatty acids (soaps), and extreme pressure additives.

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

Detergents that may be used include neutral calcium sulfonate detergents, neutral magnesium sulfonate detergents, overbased calcium sulfonate detergents, overbased magnesium sulfonate detergents, neutral calcium phenate detergents, neutral magnesium phenate detergents, overbased calcium phenate detergents, overbased magnesium phenate detergents, neutral calcium salicylate detergents, neutral magnesium salicylate detergents, overbased calcium salicylate detergents, overbased magnesium salicylate detergents, sodium sulfonate detergents, and lithium sulfonate detergents.

Any type of polymer viscosity index modifier can be used. Examples include polymers based on Olefin Copolymers (OCP), Polyalkylmethacrylates (PAMA), Polyisobutylenes (PIB), styrene block polymers (e.g., styrene isoprene, styrene butadiene), and ethylene alpha-olefin copolymers.

Additional molybdenum-based friction modifiers may be used to supplement or enhance the overall performance of such 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, oxymolybdenum sulfide dithiocarbamates, sulfur-and molybdenum-containing compounds, molybdenum dithiophosphates, oxymolybdenum sulfide dithiophosphates, tetraalkylammonium thiomolybdates, molybdenum xanthates, molybdenum thioxanthates, imidazolium oxysulfamoylates, and quaternary ammonium oxysulfamoates. Typical treat rates for molybdenum-based friction modifiers range from 50ppm to 800ppm of molybdenum delivered to the final lubricant formulation.

It is preferred that no additives such as glycerol monooleate and organic friction modifiers derived from fatty oils and diethanolamine are present, because as will be demonstrated, these types of organic friction modifiers are highly corrosive to copper and lead, as determined by the high temperature corrosion bench test (HTCBT, ASTM D6594).

Preferred antiwear additives that may be used include zinc primary and/or secondary dialkyldithiophosphates (ZDDP), triphenyl phosphorothionates, salts of dialkylphosphoric acids, salts of monoalkylphosphoric acids, salts of dialkyldithiophosphoric acids succinates, dithiophosphoric acids or carboxylic acids, trialkyl borates, borates of fatty acid derivatives, and methylenebis (dibutyldithiocarbamate).

Preferred antioxidants which 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-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, 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, derivatives of benzotriazole, derivatives of tolutriazole (tolytriazole), derivatives of triazole, dimercaptothiadiazole derivatives, fatty acid derivatives of 4, 5-dihydro-1H-imidazole, neutral calcium dinonylnaphthalenesulfonate, neutral zinc dinonylnaphthalenesulfonate, and neutral alkaline earth metal sulfonates.

Preferred extreme pressure additives that may be used include sulfurized isobutylene, sulfurized alpha-olefins, aliphatic amine phosphates, aromatic amine phosphates, dimercaptothiadiazole derivatives, zinc dialkyldithiocarbamate, dialkyl ammonium dialkyldithiocarbamate, and antimony dialkyldithiocarbamate.

The treat level of all of the above additives can vary significantly depending on the application, additive solubility, base fluid type, and finished fluid performance requirements. Typical treat levels typically vary between 0.05 wt.% to 10.00 wt.% based on the type of finished lubricant developed. The base fluid may comprise a petroleum-based or synthetic feedstock, including any fluid falling within the API base stock classifications such as class I, class II, class III, class IV, and class V. Synthetic fluids include poly-alpha-olefins, polyols, esters, bio-based lubricants, and any combination of these. The lubricating base oil or fluid is present at least 80% of the total lubricating composition.

Examples of the types of finished lubricants that may be developed using the additives of the present invention include gasoline engine oils, heavy duty diesel engine oils, natural gas engine oils, medium speed diesel (railway and marine) engine oils, off-road engine oils, two-stroke and four-stroke motorcycle engine oils, hybrid vehicle engine oils, tractor oils, auto racing oils, hydraulic fluids, automatic and manual transmission fluids, industrial and engine gear oils and greases.

The results of the performance evaluation of the inventive examples and comparative examples are described in examples 10 to 13. In examples 10 to 12, inventive examples and comparative examples were blended into SAE 0W-20 passenger car motor oil (0W-20PCMO) at the treat rates shown in tables 1 to 6. The oil was fully formulated except that it did not contain an organic or organometallic Friction Modifier (FM). In example 13, inventive and comparative examples were blended into a commercial CK-4 equivalent SAE 15W-40 heavy duty diesel engine oil (15W-40HDDEO) at the treat rates shown in Table 7.

Example 10

Tribological performance testing by SRV

The test method described for ASTM D5707 (standard test method for measuring the friction and wear characteristics of greases using a high frequency linear oscillation (SRV) tester) was followed to generate the performance data contained in table 1. The results clearly show that the examples of the present invention all provide improved wear protection and friction performance compared to the 0W-20PCMO reference oil without the organic or organometallic friction modifier. Furthermore, all four inventive examples meet or exceed the friction performance of cex.1 (a traditional organic friction modifier) while providing better wear protection, as evidenced by the inventive examples having a wear volume 9% to 27% lower than cex.1. Furthermore, the two inventive examples ex.1 and ex.7 provided an average lower friction than cex.2, with a treat rate delivering the same amount of molybdenum.

Table 1: tribological Performance testing by SRV (ASTM D5707)

Example 11

Tribological performance testing by four-ball wear

The test method described for ASTM D4172B, a standard test method for wear protection characteristics of lubricating fluids (four ball method), was followed to generate the performance data contained in table 2. According to the results of the four ball test, all four inventive examples show a favorable reduction in the average coefficient of friction compared to the 0W-20PCMO reference oil without the friction modifier. In addition, all of the inventive examples met or significantly improved the wear protection of the 0W-20PCMO reference oil as indicated by the wear scar diameter. By this test method ex.8 of the invention provides the same friction and wear performance as the two comparative examples.

Table 2: tribological Performance testing by 4-ball wear (ASTM D4172B)

Example 12

Tribological performance testing by means of a small tractor

Boundary lubrication with a "ball-and-disk" configuration and the friction characteristics of the lubricant in a mixed lubrication regime (Stribeck Curve) were evaluated using a small tractor (MTM). The MTM consists of a rotating 52100 steel ball that presses against a separately rotating 52100 steel disk immersed in a lubricant. The operating conditions are set by independently controlling the rotational speed of the shafts of the drive balls and discs in order to obtain a specific combination of rolling speed and slip-to-roll ratio, and by controlling the contact force and the oil bath temperature. The test method parameters used to generate the friction performance data contained in tables 3-6 from a small tractor (MTM) were as follows: 35N load (-1 GPa), 50% slip-to-roll ratio, speed running from 3000mm/s to 10m/s, 52100 steel. Three stribeck curves were generated at 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 140 ℃ for each formulation.

The data in table 3 relate to the friction coefficient of each oil under boundary lubrication conditions. According to the data, all four inventive embodiments provide improved boundary lubrication at temperatures of 100 ℃ or above 100 ℃ compared to the 0W-20PCMO reference oil without the organic or organometallic friction modifier. In particular, ex.1 of the present invention provides an improvement in boundary lubrication state at temperatures as low as 80 ℃. In addition, ex.1 of the present invention matched or modestly improved the friction performance of the comparative examples at 100 ℃ or above 100 ℃. Table 4 contains the results of the stirling beck coefficient of the oils obtained at each temperature. All of the inventive examples significantly improved the tribological properties of the oil compared to the 0W-20PCMO reference oil for temperatures at or above 100 ℃. Similar to the friction data in the boundary lubrication regime, the oil containing ex.1 of the present invention provided a significantly lower stirling coefficient than each of the other friction modifier additives evaluated at temperatures between 100 ℃ and 140 ℃ and inferior in performance to cex.2 at 80 ℃. These results show that ex.1 of the present invention improves not only the friction performance in the boundary lubrication state but also the friction performance in the mixed state and elastohydrodynamic state.

TABLE 3 tribological Performance testing by MTM

The reported coefficients are the average of three runs. The boundary coefficient is the coefficient of friction at a speed of 10 mm/s.

Table 4: tribological Performance testing by MTM

The strobeck coefficient was calculated by integrating the strobeck curve at each individual temperature.

The data in table 5 refer to the friction coefficient of the oil containing ex.3 or ex.9 of the present invention in the boundary lubrication state. For this study, the additive treat rate was varied to deliver between 60ppm and 900ppm molybdenum to the finished fluid. According to the data, both inventive embodiments provide improved boundary lubrication at temperatures of 80 ℃ or above 80 ℃ compared to a 0W-20PCMO reference oil without an organic or organometallic friction modifier. Even at the lowest treat rate (60ppm Mo), a modest improvement in the boundary coefficient of friction was observed for both inventive examples. A significant reduction in boundary friction is obtained once the molybdenum treat rate is 200ppm to 600 ppm. The formulations containing ex.3 of the invention demonstrate excellent performance improvements especially at the highest temperatures and handling rates. For example, formulations containing 750ppm to 900ppm molybdenum have a boundary coefficient of friction that is about 50% lower than a reference oil without any friction modifier at an operating temperature of 140 ℃. Table 6 contains the results of the strobeck coefficient of the oil at each temperature and treat rate. Furthermore, the data show that formulations containing any of the examples of the invention provide lower friction at temperatures at or above 80 ℃ at all treat rates compared to the 0W-20 reference oil without the friction modifier. In particular, ex.3 of the invention consistently results in lower strorbek coefficients at all process rates once the temperature is at 60 ℃ or above 60 ℃. As with the boundary coefficient of friction, a significant improvement in friction, evidenced by a lower strorbek coefficient, was observed for formulations containing at least 450ppm molybdenum (total treat rate of 0.74 wt.%). In addition, the total treat rate was approximately equal to the total treat rate for the comparative organic friction modifier cex.1 (see results in table 4 for 0.80 wt.% cex.1). Both formulations containing 450ppm Mo from ex.3 or ex.9 were consistently better than cex.1 at each operating temperature evaluated. Furthermore, as the treatment rate of molybdenum increased, additional improvements were observed. In particular, the strobeck coefficient of the formulation containing 750ppm Mo from ex.3 of the invention is about 55% lower than the reference oil containing neither organic nor organometallic friction modifiers at 120 ℃ to 140 ℃. The data in tables 5 and 6 again show that the examples of the present invention are effective friction modifiers over a wide range of treat rates and temperatures, as well as under boundary and mixed lubrication conditions.

Table 5: tribological performance testing by MTM at variable treat rates

The reported coefficients are the average of three runs. The boundary coefficient is the coefficient of friction at a speed of 10 mm/s.

Table 6: tribological performance testing by MTM at variable treat rates

The strobeck coefficient was calculated by integrating the strobeck curve at each individual temperature.

Example 13

Copper and lead corrosion testing by High Temperature Corrosion Bench Test (HTCBT)

The test method described for ASTM D6594 (standard test method for evaluating the corrosivity of diesel engine oils at 135 ℃) was followed to generate the copper and lead corrosion data contained in table 7. For API CK-4 class and equivalent oils, the limit by HTCBT is a maximum of 20ppm for copper, a maximum of 120ppm for lead, and a maximum of 3 copper ratings. As is clear from the data presented in table 7, the inclusion of cex.1 as an organic friction modifier additive in 15W-40HDDEO resulted in significant amounts of copper and lead corrosion. The formulations containing cex.1 are pure ester-based additives that are ineffective against copper corrosion and severely ineffective against lead corrosion. Alternatively, cex.2 is an organomolybdenum additive having an organic component that includes a mixture of an amide-based compound and an ester-based compound. For cex.2, the oil is now corroded by copper at a lower molybdenum treat rate. At higher treat rates, cex.2 provided an equivalent amount of total additive as compared to cex.1. Although cex.2 still resulted in severe failure for copper and lead corrosion, the observed lead values have decreased by over 60%. Embodiments of the present invention are organomolybdenum additives having an organic component consisting only of amide-based ligands. When ex.1 of the present invention is compared to cex.2, ex.1 shows a significant reduction in both copper and lead corrosion. Ex.1 passed through HTCBT for copper at low and high treat rates and through HTCBT for lead at lower treat rates. At both treat rates, ex.1 of the present invention showed about 67% reduction in lead corrosion compared to cex.2. The present invention ex.2 shows a two-fold increase in molybdenum content in the additive compared to ex.1. HTCBT results from Ex.2 indicate reliable passing values for copper and lead at two treatment rates. These improvements are further extended with ex.3 of the present invention, which represents a three-fold increase in molybdenum content in the additive compared to ex.1. In addition, the results from HTCBT show a significant reduction in both copper and lead corrosion values. At higher molybdenum treat rates, the lead results for ex.3 were more than 90% lower than cex.2 and more than 96% lower than cex.1. Finally, ex.9 of the present invention represents organomolybdenum compounds containing fully saturated amide-based organic ligands. The results for HTCBT of ex.9 indicate that the additive does not cause copper corrosion at all, as evidenced by the equivalent copper values and ratings compared to the reference oil. Furthermore, the formulation containing ex.9 resulted in only a very small increase in lead value at both treatment rates. The results show that ex.9 and to a lesser extent ex.2 and ex.3 can be used to deliver more molybdenum at higher treat rates if desired in terms of tribological or wear properties.

Table 7: copper and lead corrosion testing by HTCBT (ASTM D6594)

Copper and lead values are the average of at least two runs. If repeated runs result in different copper ratings, both ratings are provided.

The results of the friction performance, wear protection and corrosion tests indicate that the embodiments of the present invention represent a new class of additives that can meet or exceed the friction and wear performance of conventional additives while significantly reducing the severity of copper and lead corrosion observed.