RU2800545C2 - Less corrosive organic compounds as lubricant additives - Google Patents

Abstract

FIELD: lubricants.

SUBSTANCE: present invention relates to a composition for use as a lubricating composition, to a lubricating composition, as well as to a method for making a lubricant additive. The proposed composition for use as a lubricant composition comprises a compound selected from the following compounds: N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]isostearamide; 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. The proposed lubricant composition comprises at least 80%wt. lubricating base oil and 0.01-5%wt. additive compound represented by the formula:. In this formula, R¹ is an unsaturated or branched hydrocarbon chain comprising 1 to 21 carbon atoms, R² is a hydrogen atom or a hydrocarbon chain comprising 1 to 20 carbon atoms, and m and n are independently a number from 1 to 5, where % wt. calculated based on the total weight of the lubricant composition.

EFFECT: development of less corrosive, highly effective organic compounds with the use of additives in lubricants.

5 cl, 7 tbl, 11 ex

Description

BACKGROUND OF THE INVENTION

The field of technology to which the invention belongs

This invention includes the development of less corrosive, high performance organic compounds for use as lubricant additives. Lubricants containing these compounds have shown improved performance in reducing friction, protecting against wear and corrosion of copper and lead. In particular, the compounds of the invention are N-[3-[(2,3-dihydroxypropyl)(3-alkoxypropyl)amino]propyl]alkylamides, and unsaturated or branched N-[2-[(2,3-dihydroxypropyl)(2 -hydroxyethyl)amino]ethyl]alkylamides.

The claimed compounds represent a new class of additives capable of meeting or exceeding the friction and wear characteristics of traditional additives while significantly reducing the observed corrosion of copper and lead. This class of compounds of the invention is particularly useful in both passenger car and heavy duty diesel engine oils where high performance, longer lasting friction modifiers and/or antiwear additives are required in terms of oxidation and hydrolysis stability. .

Description of the prior art

In the prior art, DE1061966 and JP35012097 generally refer to this class of compounds. However, neither unsaturated nor branched examples of N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]alkylamides are contemplated; there is also no discussion of N-[3-[(2,3-dihydroxypropyl)(3-alkoxypropyl)amino]propyl]alkylamides. In addition, neither DE1061966 nor JP35012097 provide for the use of this class of compounds in lubricants as friction modifying or wear protection additives.

DE 1061966 describes the preparation of related 2,3-dihydroxy compounds by reacting an alkylamide intermediate, N-[2-[(2-hydroxyethyl)amino]ethyl]- with b-chlorohydrin or epichlorohydrin. This process may require the use of caustic bases and generate halogenated waste. In the invention presented herein, the alkylamidamine intermediates are instead reacted with glycidol in the presence of ethanol. These reactions have the advantage of being completely economical and generating no waste. Ethanol can be isolated from the reaction mixture by simple distillation and recycled to the process.

US5397486 describes a reaction in which glycidol adducts differ from those used in the reaction to form the compounds of the invention. This reference uses glycidol adducts where X is oxygen, sulfur or nitrogen and R is a hydrocarbyl radical containing 4-50 carbon atoms, of the following formula:

The class of compounds of the invention is chemically distinct and outside the scope of the class described in US5397486. In addition, US5397486 describes lubricant compositions containing the above class of compounds as silver antiwear additives specifically for diesel engine applications having engine parts with a silver surface. US9464252 describes glycidol adducts but does not discuss their role in terms of friction modifier performance, overall wear protection, or copper and lead corrosion.

US Pat. Nos. 5,560,853; 5,672,727; 9,321,976; The class of compounds of the invention is chemically distinct and outside the scope of the class described in these patents.

SUMMARY OF THE INVENTION

The class of compounds in the present invention may be represented by Formula I:

where R ¹ is a hydrocarbon chain, and R ² is a hydrogen atom or a hydrocarbon chain. The R ¹ group consists of an unsaturated and/or saturated and/or linear and/or branched hydrocarbon chain containing 1-21 carbon atoms. Preferably the R ¹ group is unsaturated or branched. It is further preferred that the R ¹ group be both saturated and branched. It is also preferred that the R ¹ group consists of a hydrocarbon chain containing 11-21 carbon atoms. The group R ² may be a hydrogen atom or a linear, cyclic or branched hydrocarbon chain containing 1-20 carbon atoms. The number of methylene spacer groups ( n and m ) is independently 1 to 5 at each occurrence. Preferably, the number of methylene spacer groups ( n and m ) is independently 2 or 3 at each occurrence.

This class of compounds can be obtained in accordance with the general reaction scheme I:

In the first step, a carbonyl-containing compound, such as a carboxylic acid, a carboxylic acid ester, or a triglyceride, is reacted with a mixed primary/secondary amine-containing compound to form a secondary amide. In the second step, the secondary amide intermediate is further reacted with glycidol to form the final product described in formula I. The second step can be carried out in the presence of a protic solvent such as methanol or ethanol to increase the efficiency of the reaction.

As emphasized above, the class of compounds in this invention can also be described as reaction products of (a) a carboxylic acid or ester or triglyceride, (b) a mixed primary/secondary amine compound, and (c) glycidol. Non-limiting examples of compounds of this 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]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-decyloxypropyl)amino]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 two-step procedure is representative of the class of compounds described in the present invention: 664 mmol of oleic acid is added to a three-neck flask equipped with a temperature probe, a mechanical stirrer and a distillation trap equipped with a condenser. 664 mmol of 2-aminoethylethanolamine is added to the flask and the reaction mixture is placed under a nitrogen atmosphere. The reaction mixture is heated to 150°C and the resulting water is collected in a distillation trap. After heating for about 6 hours, the reaction mixture is cooled and the amide product is used directly in the next step without purification.

271 mmol of the product from the previous step is added to a three-necked flask equipped with a temperature probe and a mechanical stirrer. Add 275 ml of ethanol to the flask and connect the reflux condenser. A solution consisting of 258 mmol glycidol in 70 ml ethanol is prepared and transferred to an addition funnel with a nitrogen inlet attached to the top of the reflux condenser. The reaction mixture is placed under a nitrogen atmosphere and heated until condensation appears (approximately 80°C). The glycidol solution is added dropwise to the flask over 30 minutes. After addition is complete, the reaction mixture is heated with a reflux condenser for an additional 6 hours. The reaction mixture is concentrated by rotary evaporation until all ethanol has been removed to give the desired product.

Various starting materials can be used in the above reactions as shown in General Reaction Scheme I. In the first step, a carbonyl-containing compound such as a carboxylic acid, a carboxylic acid ester or a triglyceride can be used. For carboxylic acids, the group R ¹ consisting of 1-21 carbon atoms may be a linear, cyclic or branched saturated hydrocarbon or unsaturated and/or polyunsaturated hydrocarbon, or mixtures thereof. For esters of carboxylic acids, the group R ¹ consisting of 1-21 carbon atoms, may be a linear, cyclic or branched saturated hydrocarbon or unsaturated and/or polyunsaturated hydrocarbon, or mixtures thereof. For triglycerides, the R ¹ group of 1-21 carbon atoms may be a linear, cyclic or branched saturated hydrocarbon or an unsaturated and/or polyunsaturated hydrocarbon, 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 moles of carboxylic acid or carboxylic acid ester per 1.0 moles of primary amine containing 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 are generally not necessary or preferred. Preferred carboxylic acid esters are fatty acid methyl esters (FAME) and fatty acid ethyl esters, also referred to as biodiesel. The sources of biodiesel are the fatty oils described below. For the reaction of a triglyceride with a primary amine compound, the reaction stoichiometry can be varied such that 1.0 mole of triglyceride reacts with 1.0-3.0 mole of the primary amine compound to produce 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 compounds can be derived from fatty oils such as coconut oil, hydrogenated coconut oil, fish oil, hydrogenated fish oil, animal fat, hydrogenated animal fat, corn oil, rapeseed oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, sunflower oil, canola oil and soybean oil. For a mixed primary/secondary amine compound, the R ² group may be a hydrogen atom or a linear, cyclic or branched hydrocarbon chain containing 1-20 carbon atoms, or mixtures thereof, and the number of methylene spacer groups ( n and m ) may vary from 1 to 5.

Compounds of the following examples were prepared using the representative procedure described above:

Example 1 (Note 1)

The procedure for preparing N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]oleamide was identical to the representative procedure.

Example 2 (Note 2)

The procedure for preparing N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]oleamide was identical to the representative procedure, except that isotridecyloxypropyl-1,3-diaminopropane was used instead of 2-aminoethylethanolamine.

Example 3 (Note 3)

The procedure for preparing N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]cocoamide was identical to the representative procedure, except that coconut oil methyl esters were used instead of oleic acid.

Example 4 (Note 4)

The procedure for preparing N-[3-[(2,3-dihydroxypropyl)(3-isotridecyloxypropyl)amino]propyl]cocoamide was identical to the representative procedure, except that coconut oil methyl esters were used instead of oleic acid, and isotridecyloxypropyl-1, 3-diaminopropane was used instead of 2-aminoethylethanolamine.

Example 5 (Note 5)

The procedure for preparing N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]isostearamide was identical to the representative procedure, except that isostearic acid was used instead of oleic acid.

The following compounds are included as comparative examples of the invention described here:

Comparative Example 1 (Compar. note 1)

Glycerol monooleate ( ^HiTEC® 7133 from Afton Chemical)

Comparative Example 2 (Compar. note 2)

Commercial organic friction modifier, consisting of the reaction products of 1.0 mol of fatty oil containing 12 or more carbon atoms and 1.0-2.5 mol of diethanolamine.

Individual compounds from the class of substances of the invention may be used as lubricant additives to reduce friction and/or as additional wear protection at a dosage of from about 0.01-5.00% by weight, preferably about 0.10-3 00%, and more preferably about 0.20-2.00%, and even more preferably about 0.40-1.00%, as a percentage by weight of the entire lubricant composition. In addition, these compounds can 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 monosuccinimide dispersants, polyisobutylene disuccinimide dispersants, polypropylene monosuccinimide dispersants, polypropylene disuccinimide dispersants, ethylene propylene copolymer monosuccinimide dispersants, ethylene propylene copolymer disuccinimide dispersants, Mannich dispersants, dispersant ant olefin copolymers oxidant, succinimide dispersants of low molecular weight ethylene and propylene, carboxyl dispersants, amine dispersants, borated dispersants and molybdenum-containing dispersants.

Detergents that can be used include neutral calcium sulfonate detergents, neutral magnesium sulfonate detergents, high alkaline calcium sulfonate detergents, high alkaline magnesium sulfonate detergents, neutral calcium phenolate detergents, neutral magnesium phenolate detergents, high alkaline calcium phenolate detergents, high alkaline magnesium phenolate detergents, neutral detergents salicylate tergents calcium, neutral magnesium salicylate detergents, high alkaline calcium salicylate detergents, high alkaline magnesium salicylate detergents, sodium sulfonate detergents, and lithium sulfonate detergents.

Any type of polymeric viscosity index modifier can be used. Examples include polymers based on olefin copolymers (OCP), polyalkyl methacrylates (PAMA), polyisobutylenes (PIB), styrenic block copolymers (such as isoprene-styrene, butadiene-styrene), and ethylene-alpha-olefin copolymers.

Molybdenum based friction modifiers can be used to supplement or enhance the overall performance of the class of compounds in this invention. Examples of types of alternative friction modifiers that can be used, include molybdenum complexes obtained by the interaction of fatty oil, dietanolamine and molybdenum, molybdates of complex esters, single -core ditocarbamates molybdenum, dual -core ditiocarbamates of molybden oximolibden mats containing sulfur and molybdenum compounds compounds containing amine and molybdenum, molybdenum phosphorodithioates, sulfonated oxymolybdenum dithiophosphates, tetraalkylammonium thiomolybdates, molybdenum carboxylates, molybdenum xanthates, molybdenum thioxanthates, imidazolium oxythiomolybdate salts and quaternary ammonium oxythiomolybdate salts. Typical dosages of molybdenum based friction modifiers range from 50 ppm to 800 ppm molybdenum supplied to the finished lubricating composition.

Preferably, additives such as glycerol monooleate and organic friction modifiers derived from fatty oils and diethanolamine are not present because these types of organic friction modifiers will be shown to be highly corrosive to copper and lead as determined by bench tests. for high temperature corrosion (HTCBT, ASTM D6594). Accordingly, the invention also includes a lubricant composition free of glycerol monooleate and organic friction modifiers derived from fatty oils and diethanolamine.

Preferred anti-wear 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 acid or carboxylic acid esters, trialkyl borate esters, borate esters fatty acid derivatives and methylenebis(dibutyldithiocarbamate).

Preferred antioxidants that may be used include dinonyldiphenylamine, monononyldiphenylamine, dioctyldiphenylamine, monooctyldiphenylamine, butyloctyldiphenylamine, monobutyldiphenylamine, dibutyldiphenylamine, nonylated phenyl alpha naphthylamine, octylated phenyl alpha naphthylamine, dodecyl phenyl alpha naphthylamine, 2,6-di-tr no -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 thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

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

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

The dosages of all of the additives described above can vary considerably depending on the application, the solubility of the additive, the type of base fluid, and the performance requirements of the final fluid. Typical dosages typically range from 0.05% wt. up to 10.00% wt., depending on the type of final lubricating oil being developed. Base fluids may include petroleum-based or synthetic components, including any fluid that falls within the API classification for base stocks as Group I, Group II, Group III, Group IV, and Group V. Synthetic fluids include poly-α-olefins , polyols, esters, bio-based lubricants, and any combination thereof. The lubricating base oil is present in an amount of at least 80% of the total lubricating composition.

The results of the performance evaluations for the Inventive Examples and Comparative Examples are described in Examples 6-9. In examples 6-8, the compounds of the examples of the invention and comparative examples were mixed with motor oil for passenger cars SAE 0W-20 (0W-20 PCMO) in dosages of 0.40-1.00 wt%. This oil was fully formulated, except that it excluded the organic or organometallic friction modifier (FM). In Example 9, compounds of the Inventive Examples and Comparative Examples were mixed with a commercial CK-4 equivalent of SAE 15W-40 Heavy Duty Diesel Engine Oil (15W-40 HDDEO) at a dosage of 0.75 wt%.

Example 6

Tribological performance testing with SRV

The test method described for ASTM D5707 (Standard Test Method for Measuring Friction and Wear Properties of Lubricating Greases Using a High Frequency Linear Vibration Testing Machine (SRV)) was used to obtain the performance characteristics contained in Table 1. The results presented in Table 1 are clearly indicate that both the compounds of the Inventive Examples and Comparative Examples provided additional wear protection as evidenced by lower wear volumes compared to the FM-free reference 0W-20 PCMO oil. The improvements obtained in the examples according to the invention provided a reduction in the amount of wear by 40-56%. In addition, Prim. 2 and Note. 4 of the invention provided a slight improvement in average coefficients of friction compared to the PCMO 0W-20 reference oil.

Table 1: Tribological Performance Testing with SRV (ASTM D5707)

Additive Dosage FM (% wt.) Wear volume (µm ³ ) Average coefficient of friction 0W-20 PCMO 0 54055 0.144 + Comp. approx. 1 0.80 41699 0.132 + Comp. approx. 2 0.80 15145 0.140 + Approx. 1 0.80 32387 0.144 + Approx. 2 0.80 23690 0.137 + Approx. 3 0.80 24121 0.152 + Approx. 4 0.80 26987 0.138

Example 7

Testing tribological performance in a four-ball wear test

The test method described for ASTM D4172 B (Standard Test Method for Measuring Anti-Wear Characteristics of Lubricating Fluids (Using a Four-Ball Machine)) was used to obtain the performance characteristics contained in Table 2. Under these test conditions, all four examples of the invention provided lower average coefficients friction compared to reference oil 0W-20 PCMO free of FM. In addition, Prim. 2 and Note. 4 provided improved wear protection as evidenced by the reduced wear scar diameter.

Table 2. Tribological performance testing with a four-ball machine (ASTM D4172 B)

Additive Dosage FM (% wt.) Wear scar diameter (mm) Average coefficient of friction 0W-20 PCMO 0 0.45 0.099 + Comp. approx. 1 0.80 0.34 0.062 + Comp. approx. 2 0.80 0.34 0.066 + Approx. 1 0.80 0.43 0.094 + Approx. 2 0.80 0.34 0.062 + Approx. 3 0.80 0.45 0.086 + Approx. 4 0.80 0.36 0.079

Example 8

Tribological Performance Testing with Mini Traction Machine (MTM)

A mini traction machine (MTM) was used to evaluate the frictional performance of lubricants in boundary and mixed lubrication conditions (Stribeck curve) with a ball-on-disk configuration. The MTM includes a rotating 52100 steel ball pressed against an independently rotating 52100 steel disc immersed in lubricant. Operating conditions are set by independently adjusting the rotational speeds of the shafts driving the ball and disc to obtain a specific combination of rolling speed and slip-to-roll ratio, and by adjusting the contact force and oil bath temperature. The test method parameters used to obtain the friction performance data contained in Tables 3-6 as a result of using a Mini Traction Machine (MTM) are as follows: load 35 N (~ 1 GPa), slip:roll ratio 50%, speed strokes from 3000 mm/s to 10 mm/s, steel 52100. For each composition, three Stribeck curves were obtained at 40°C, 60°C, 80°C, 100°C, 120°C and 140°C. The average of the three runs was noted for each temperature.

Table 3 shows the marginal friction coefficient improvements for the inventive examples compared to the FM-free reference oil 0W-20 PCMO. In particular, as soon as the temperature reached or exceeded 80°C, all five examples according to the invention provided lower boundary coefficients. Most notably, in approx. 1 according to the invention, the lowest limiting coefficient of friction at temperatures of 60°C and above was noted for all the evaluated additives. Table 4 shows the results for the Stribeck coefficients obtained for oils at each temperature. For temperatures at or above 100° C., all examples of the invention significantly improved the frictional characteristics of the oil compared to the FM-free formulation. It should be noted that both examples according to the invention, Approx. 1 and Note. 5 provided lower Stribeck coefficients at temperatures of 60°C or higher than the reference oil without friction modifier and oils containing compounds of any comparative example. Similar to the friction data in the boundary lubrication mode, the oil containing the composition of Approx. 1 of the invention provided significantly lower Stribeck coefficients than any other friction modifier evaluated at temperatures of 80-140°C. These results show that Approx. 1 according to the invention not only improves frictional characteristics in the boundary lubrication mode, but also in mixed and elastohydrodynamic modes.

Table 3. Tribological Performance Testing with MTM

Limiting coefficient of friction* at a given temperature Additive Dosage FM (% wt.) 40°C 60°C 80°C 100°C 120°C 140°C 0W-20 PCMO 0 0.076 0.094 0.113 0.128 0.127 0.128 + Comp. approx. 1 0.80 0.091 0.095 0.090 0.090 0.088 0.077 + Comp. approx. 2 0.80 0.102 0.107 0.110 0.104 0.103 0.105 + Approx. 1 0.80 0.086 0.093 0.090 0.086 0.079 0.075 + Approx. 2 0.80 0.089 0.098 0.100 0.097 0.098 0.098 + Approx. 3 0.80 0.084 0.110 0.101 0.109 0.098 0.086 + Approx. 4 0.80 0.092 0.103 0.106 0.100 0.096 0.093 + Approx. 5 0.80 0.079 0.096 0.103 0.097 0.089 0.082

*Coefficients shown are the average of three runs. The limit factor is the coefficient of friction at a speed of 10 mm/s.

Table 4. Tribological Performance Testing with MTM

Stribeck coefficient* at a given temperature Additive Dosage FM (% wt.) 40°C 60°C 80°C 100°C 120°C 140°C 0W-20 PCMO 0 0.135 0.141 0.167 0.219 0.268 0.278 + Comp. approx. 1 0.80 0.142 0.156 0.168 0.180 0.191 0.181 + Comp. approx. 2 0.80 0.160 0.158 0.159 0.159 0.172 0.198 + Approx. 1 0.80 0.145 0.138 0.133 0.134 0.134 0.138 + Approx. 2 0.80 0.148 0.152 0.161 0.172 0.197 0.218 + Approx. 3 0.80 0.141 0.169 0.176 0.196 0.201 0.196 + Approx. 4 0.80 0.149 0.152 0.164 0.170 0.178 0.184 + Approx. 5 0.80 0.134 0.135 0.140 0.144 0.157 0.163

*Stribeck coefficients are calculated by integrating the Stribeck curve for each individual temperature.

Table 5 further shows the marginal friction coefficient improvements for the inventive examples compared to the PCMO 0W-20 reference oil, which does not contain a friction modifier. These studies evaluated formulations containing compositions of the Inventive Examples or Comparative Examples at three different dosages. From the data presented in Table 5, at temperatures of 80° C. or higher, all three examples of the invention provided lower cut-off factors than the reference oil without any FM, even at the lowest dosage (0.40% wt.). Table 6 shows the results for the Stribeck coefficients obtained for oils at each temperature and dosage. Again, once operating temperatures were at or above 80 ° C, all three examples of the invention at each dosage showed improved friction compared to the FM-free reference oil 0W-20, as evidenced by the lower Stribeck coefficients. As in the case of the data given in table 4 above, the compositions containing the composition Approx. 1 according to the invention showed exceptional friction reduction, especially at higher operating temperatures and dosages. In particular, Note. 1 of the invention provided the lowest observed Stribeck ratios for any of the additives rated in the 100-140 ° C range at the highest dosage. These data in Table 5 and Table 6 again indicate that Approx. 1 according to the invention not only improves frictional characteristics in the boundary lubrication mode, but also in mixed and elastohydrodynamic modes for the entire range of dosages.

Table 5. Tribological performance testing with MTM at additional dosages

Limiting coefficient of friction* at a given temperature Additive Dosage FM (% wt.) 40°C 60°C 80°C 100°C 120°C 140°C 0W-20 PCMO 0 0.076 0.094 0.113 0.128 0.127 0.128 + Comp. approx. 1 0.40 0.078 0.086 0.085 0.077 0.074 0.064 + Comp. approx. 2 0.40 0.092 0.101 0.095 0.089 0.086 0.105 + Approx. 1 0.40 0.091 0.096 0.098 0.092 0.085 0.080 + Approx. 2 0.40 0.088 0.102 0.104 0.100 0.097 0.093 + Approx. 5 0.40 0.088 0.104 0.111 0.108 0.100 0.089 + Comp. approx. 1 0.60 0.072 0.075 0.078 0.076 0.072 0.067 + Comp. approx. 2 0.60 0.094 0.102 0.097 0.094 0.090 0.082 + Approx. 1 0.60 0.091 0.098 0.098 0.090 0.083 0.084 + Approx. 2 0.60 0.084 0.098 0.105 0.104 0.099 0.091 + Approx. 5 0.60 0.097 0.106 0.109 0.104 0.098 0.092 + Comp. approx. 1 1.00 0.079 0.083 0.082 0.077 0.075 0.071 + Comp. approx. 2 1.00 0.086 0.093 0.098 0.093 0.081 0.085 + Approx. 1 1.00 0.087 0.094 0.096 0.086 0.077 0.069 + Approx. 2 1.00 0.089 0.095 0.103 0.098 0.094 0.092 + Approx. 5 1.00 0.092 0.101 0.103 0.100 0.094 0.086

*Coefficients shown are the average of three runs. The limit factor is the coefficient of friction at a speed of 10 mm/s.

Table 6: Tribological performance testing with MTM at additional dosages

Stribeck coefficient* at a given temperature Additive Dosage FM (% wt.) 40°C 60°C 80°C 100°C 120°C 140°C 0W-20 PCMO 0 0.135 0.141 0.167 0.219 0.268 0.278 + Comp. approx. 1 0.40 0.135 0.138 0.146 0.155 0.159 0.148 + Comp. approx. 2 0.40 0.142 0.149 0.157 0.162 0.170 0.202 + Approx. 1 0.40 0.139 0.143 0.154 0.161 0.168 0.177 + Approx. 2 0.40 0.146 0.148 0.157 0.166 0.181 0.195 + Approx. 5 0.40 0.145 0.151 0.167 0.181 0.195 0.201 + Comp. approx. 1 0.60 0.129 0.126 0.130 0.137 0.143 0.139 + Comp. approx. 2 0.60 0.143 0.155 0.162 0.173 0.185 0.180 + Approx. 1 0.60 0.148 0.143 0.144 0.144 0.146 0.153 + Approx. 2 0.60 0.143 0.143 0.155 0.165 0.178 0.191 + Approx. 5 0.60 0.154 0.154 0.157 0.160 0.169 0.184 + Comp. approx. 1 1.00 0.132 0.129 0.135 0.141 0.150 0.145 + Comp. approx. 2 1.00 0.133 0.132 0.137 0.144 0.139 0.148 + Approx. 1 1.00 0.145 0.137 0.137 0.129 0.122 0.118 + Approx. 2 1.00 0.145 0.142 0.149 0.163 0.168 0.186 + Approx. 5 1.00 0.147 0.143 0.142 0.142 0.144 0.153

*Stribeck coefficients are calculated by integrating the Stribeck curve for each individual temperature.

Example 9

Copper and Lead Corrosion Testing with High Temperature Corrosion Bench Testing (HTCBT)

The test method described for ASTM D6594 B (Standard Test Method for Evaluating the Corrosivity of Diesel Lubricating Oil at 135°C) was used to obtain the copper and lead corrosion data contained in Table 7. For API CK-4 oils and equivalent oils, the limits for passing HTCBT were 20 ppm maximum for copper, 120 ppm maximum for lead, and 3 corrosion points maximum for copper. From the data presented in Table 7, the Inventive Examples provide significant improvements over the Comparative Examples with respect to copper and lead corrosion. The data clearly indicate that the inclusion of the composition cf. approx. 1 as an FM additive in 15W-40 HDDEO results in a significant amount of corrosion on both copper and lead. Composition containing comp. approx. 1, which is a pure ester additive, fails to cope with copper corrosion and seriously fails to cope with lead corrosion. Alternatively, compare approx. 2 is a mixture of compounds based on both amides and esters. For comparison. approx. 2 The oil is now being tested for copper corrosion. While the oil containing cf. approx. 2 still leads to severe corrosion of lead, the observed values for lead are reduced by more than 70%. The examples of the invention are exclusively based on amides. For Note. 1, the composition passes for copper corrosion and is marginal for lead corrosion. However, formulations containing Ex. 2 or Ex. 5 of the invention pass both copper and lead corrosion and also match the copper corrosion score of the reference 15W-40 HDDEO. Note. 2 and Note. 5 according to the invention compared with comp. approx. 1 give a reduction in copper corrosion by 75% and lead corrosion by almost 90%. In addition, Prim. 2 and Note. 5 according to the invention have the advantage of reducing lead corrosion by more than 60% compared to comp. note 2.

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

Additive Dosage FM (% wt.) Cu (ppm)* Corrosion score Cu Pb (ppm)* 15W-40 HDDEO 0 6.0 1b 7.5 + Comp. approx. 1 0.75 40.0 2e 925.0 + Comp. approx. 2 0.75 6.0 1b 270.0 + Approx. 1 0.75 14.5 1b 145.0 + Approx. 2 0.75 10.0 1b 103.5 + Approx. 5 0.75 11.0 1b 103.0

*Average of at least two runs.

The results of frictional performance, wear protection and corrosion tests show that the examples of the invention represent a new class of additives capable of meeting or exceeding the friction and wear characteristics of traditional additives while significantly reducing the observed corrosion of copper and lead.

Claims (19)

1. The composition of the substance for use as a lubricant composition, where the composition contains a compound selected from the following compounds: N-[2-[(2,3-dihydroxypropyl)(2-hydroxyethyl)amino]ethyl]isostearamide; 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. 2. Lubricating composition containing at least 80% of the mass. lubricating base oil and 0.01-5% of the mass. additive compound represented by the following formula: where R ¹ is an unsaturated or branched hydrocarbon chain containing from 1 to 21 carbon atoms, R ² is a hydrogen atom or a hydrocarbon chain containing from 1 to 20 carbon atoms, and m and n are independently a number from 1 to 5, where % wt. calculated based on the total weight of the lubricating composition. 3. Lubricant composition according to claim 2, in which the additive compound is a reaction product (a) a carboxylic acid or ester; (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. 4. The lubricant composition according to claim 2, in which the additive compound is present in an amount of 0.20-2.00 wt. -%, where wt.%. calculated based on the total weight of the lubricant composition. 5. A method for manufacturing a lubricant additive represented by the following formula: where the specified additive contains at least one first compound, where R ¹ represents an unsaturated or branched hydrocarbon chain containing from 1 to 21 carbon atoms, and at least one second compound, where R ¹ represents a saturated and straight hydrocarbon chain containing from 1 to 21 carbon atoms, where R ² is a hydrogen atom or a hydrocarbon chain containing from 1 to 20 carbon atoms, and m and n independently represent a number from 1 to 5, and the method includes the stage of joint interaction: (a) mixtures of carboxylic acids or esters; (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.